Crystal Structure and Antitumor Activity of Tri[2- [N-(4''''-methyl-benzylsulfonyl)amino]ethyl]-amine

1 INTRODUCTION The supramolecular architectures of tripodal ligands with special cavities have attracted much attention of chemists and biochemists because of their interesting structures and possible properties such as ion and molecular recognition, selective inclusion and important biological function[1～5]. However, their potential applications in supra- molecular and biological chemistry for constructing various complexes have not been clearly realized until recent years. Few crystal…     

Crystal Structure and Antitumor Activity of Tri[2-[N-（4′-methyl-benzylsulfonyl）amino]ethyl]-amine

The crystal structure of the title compound (C27H38N4O7S3, Mr = 626.79) has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pīwith a = 9.411(1), b = 11.645(2), c = 14.672(2) (A。), α = 91.80(1), β = 95.36(1), γ =104.56(1)o, V = 1547.0 (A。)3, Z = 2, Dc = 1.346 g/cm3, λ = 0.71073 (A。), μ(MoKα) = 0.289 mm－1 and F(000) = 664. The structure was refined to R = 0.0406 and wR = 0.1177 for 4103 observed reflections with I > 2σ(I). X-ray diffraction analysis reveals that the title compound is a practically distorted tetrahedron and each molecule contains one lattice H2O by hydrogen bond. The antitumor activity of the title compound against HL-60 human leukemia cells has also been studied by MTT method.     

新型手性双核Salen Zn(II)配合物的分子识别研究

采用新型Salen中间体合成了新型Salen Zn(II)配合物. 用紫外-可见光谱滴定法研究了主体双核Salen Zn(II)与咪唑、二胺类等含氮小分子的分子识别行为, 测定了它们的缔合常数. 对咪唑类客体的缔合常数顺序为K^θ(Im)＞K^θ(2-MeIm)＞K^θ(EMeIm); 对二胺类客体缔合常数顺序为K^θ(DAP)＞K^θ(DAE). 主体与咪唑类和二胺类客体的配位数分别是2和1. 主体与这些客体的识别过程为放热、熵减的焓驱动反应. 利用圆二色光谱研究了识别过程的Cotton效应. 用分子力学方法研究了主客体体系的最低能量构型, 通过量化计算对实验事实做了进一步解释.     

新型手性双核Salen Zn(II)配合物的分子识别研究

采用新型Salen中间体合成了新型SalenZn(II)配合物.用紫外-可见光谱滴定法研究了主体双核SalenZn(II)与咪唑、二胺类等含氮小分子的分子识别行为,测定了它们的缔合常数.对咪唑类客体的缔合常数顺序为K(Im)>K(2?MeIm)>K(EMeIm);对二胺类客体缔合常数顺序为K(DAP)>K(DAE).主体与咪唑类和二胺类客体的配位数分别是2和1.主体与这些客体的识别过程为放热、熵减的焓驱动反应.利用圆二色光谱研究了识别过程的Cotton效应.用分子力学方法研究了主客体体系的最低能量构型,通过量化计算对实验事实做了进一步解释.     

新树型配体 TBOAA 与钴配合物的研究

研究了新配体N，N’，N”－（三苯甲酰）－三乙氨基胺（TOBAA）与二价钴离子生成配合物的光度特征和电化学特征。在较宽的pH范围内，新试剂和钴离子形成2：1的配合物，并且在一定范围内其吸光度与浓度具有良好的线性关系。     

2-[1-(2,6-Dibenzhydryl-4-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridylcobalt(II) dichlorides: synthesis, characterization and ethylene polymerization behavior

A series of unsymmetrical 2,6-bis(imino)pyridylcobalt(II) complexes, {2-[2,6-(CH(C(6)H(5))(2))(2)-4-Me-C(6)H(2)N==C(CH(3))]-6-(2,6-R(1)(2)-4-R(2)-C(6)H(2)N==CCH(3))-C(5)H(3)NCoCl(2)} where R(1) = Me, Et or (i)Pr, R(2) = H or Me, together with the new symmetrical complex 2,6-[2,6-(CH(C(6)H(5))(2))(2)-4-Me-C(6)H(2)N==C(CH(3))](2)-C(5)H(3)NCoCl(2), were synthesized. All of the compounds were fully characterized by (1)H NMR and IR spectroscopy, as well as by elemental analysis. The molecular structures of Co1 (R(1) = Me, R(2) = H) and Co5 (R(1) = Et, R(2) = Me) were further confirmed by single crystal X-ray diffraction, which indicated that the cobalt centres were penta-coordinate with a pseudo square-pyramidal geometry. Upon treatment with MAO or MMAO, these cobalt pre-catalysts exhibited higher activities than any previously reported cobalt pre-catalysts, with values as high as 4.64 × 10(6) g PE mol(-1)(Co) h(-1) for ethylene polymerization at atmospheric pressure. The polyethylenes obtained were of high molecular weight and narrow molecular weight distribution.     

Chemical transformations of 6-[(1-methyl-4-nitro-5-imidazolyl)-thio]purine (azathioprine)

The chemical transformations of 6-[(1-methyl-4-nitro-5-imidazolyl)thio]purine (azathiopurine) —hydrogenation, acetylation, alkylation by lower alkyl halides at positions 7 and 9 of the purine ring, hydrolytic cleavage at the C₍₆₎–S and S–C₍₅₎ bonds— were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 372–379, March, 2000.     

N-丁基-4-[乙基-(3-甲基苯基)氨基]丁酰胺的合成

以γ-丁内酯为起始原料,经开环氯化和酰化反应制得N-丁基-4-氯丁酰胺(2);2与N-乙基间甲苯胺经N-烷基化反应合成了N-丁基-4-[乙基-(3-甲基苯基)氨基]丁酰胺,总收率74.6%,纯度97.6%,其结构经1H NMR和MS(ESI)确证。     

Synthesis and Crystal Structure of catena-Poly[[[2,4-dibromo-6-[(3-dimethylaminopropylimino)-methyl]phenolato]copper(Ⅱ)]-μ-azido]

A novel end-to-end azido-bridged polynuclear Schiff-base copper(H) complex,[Cu(C12H15Br2N2O)(N3)]n, was prepared and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction.The crystal belongs to the orthorhombic system, space group Pbcn with a = 24.588(5), b = 10.377(2), c = 13.022(3)(A),V= 3322.6(12)(A)3, Z = 8, Dc = 1.874 g/cm3, Mr= 468.65, λ(MoKα) = 0.71073 (A),μ= 6.130 mm-1, F(000) = 1832, R = 0.0637 and wR = 0.1176.The Cu atom in the complex is five-coordinated in a square pyramidal geometry by three donoratoms of the Schiff-base ligand, and two N atoms from two bridging azide ligands.The [2,4-dibromo-6-[(3-dimethylaminopropylimino)methyl]phenolato]copper(Ⅱ) units are linked by the bridging azide ligands, giving zigzag polymeric chains with backbones of the [-Cu-N-N-N-Cu]n type running along the b axis.     

Crystal structures of nitrato-{4-bromo-2-[(2-hydroxyethylimion)methyl]phenolo}-(3,5-Dibromopyridine)copper and nitrato-{2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper

The crystal structures of nitrato-{4-bromo-2-[2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper (I) and nitrato-{2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper (II) are determined. The crystals of compound I are orthorhombic: a = 14.157(3) Å, b = 15.420(3) Å, c = 17.494(4) Å, space group Pbca, Z = 8, R = 0.067. The crystals of compound II are monoclinic: a = 10.675 Å, b = 13.973 Å, c = 14.007 Å, β = 111.92°, space group P2₁/n, Z = 4, R = 0.0464. In the structures of compounds I and II, the copper atom coordinates, correspondingly, singly deprotonated 4-bromo-2-[(2-hydroxyethylimino)methyl]phenol and 2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenol molecules, and 3,5-dibromopyridine, and the nitrate ion. The coordination polyhedron of the copper ion in complexes I and II is a slightly distorted tetragonal pyramid. The bases of the pyramids are formed by the imine and pyridine nitrogen atoms and the phenolic and alcoholic oxygen atoms, and the axial vertices are occupied by the oxygen atoms of the monodentate nitrato groups. In the complexes under study, the six-membered metallocycles have asymmetric gauche conformation. In crystal, complexes I are united, due to the slip plane a, through bifurcate hydrogen bonds into infinite chains along the direction [100]. Complexes II in crystal form two-dimensional networks by means of hydrogen bonds.     

Complex Formation in the System Bis[2-(trimethylammonio)ethyl] Succinate Diodide-Iodine in Solutions and in Crystal

The complex formation in the system bis[2-(trimethylammonio)ethyl] succinate diodide-iodine involves no more than two iodine molecules. The crystal structure of the salt [(CH3)3N(CH2)2OCOCH2]2(I3)2 is formed by layers of inorganic anions (I₃ ^-) and organic dications (centrosymmetric dications {[(CH₃)₃N · (CH₂)₂OCOCH₂]⁺}₂), evenly alternating along the a axis. The crystal structure of the salt [(CH₃)₃N(CH₂)₂·OCOCH₂]₂(I₃)₂(I₂)0.5 is formed by organic and inorganic layers evenly alternating along the [011] diagonal, with a centrosymmetric iodine molecule.     

1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲的另一个手性对映体晶体结构

对-二甲氨基苯甲醛和苯基氨基硫脲缩合反应生成1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲(DMB), 产物能从溶液中析出单一手性对映体晶体. 用单晶X射线衍射技术测定了它的绝对构型, 晶体属正交晶系, P2₁2₁2₁空间群, a＝0.7870(2) nm, b＝1.1560(2) nm, c＝1.6668(3) nm, V＝1.5164(5) nm³, Z＝4, D_c＝1.307 g/cm³, F(000)＝632, μ＝0.213 mm^－1, 2557个可观测点[I＞2s(I)]精修的最终残差因子: R＝0.0409, wR＝0.1061, Flack参数为0.00(9), 能够确定绝对构型. 化合物的晶体结构和大宗粉末样品的固体圆二色谱表明化合物在结晶过程中发生单一对映体的手性堆积.     

Molecular and electronic structures of bis(dipicolylamine)copper(II) perchlorate and bis[2-(2-pyridylethyl)picolylamine]copper(II) perchlorate

The geometric isomers of bis(dipicolylamine)copper(II) perchlorate, [Cu(dipica)₂](ClO₄)₂, and bis[2-(2-pyridylethyl)picolylamine]copper(II) perchlorate, [Cu(pepica)₂](ClO₄)₂, have been prepared and their molecular structures determined by X-ray diffraction methods. The copper atom of cis-fac-[Cu(dipica)₂](ClO₄)₂, is six coordinate with an amine nitrogen and a pyridyl group of each facial dipica ligand forming a cis coordination plane, and the remaining pyridyl nuclei on the axial sites completing a distorted octahedral structure. The mixed trans-fac- & square-pyramidal-[Cu(dipica)₂](ClO₄)₂ comprises discrete hexacoordinate and pentacoordinate cations. The distorted trans-facial octahedral cation has two picolyl chelates in the equatorial plane and two slightly longer axial pyridyl groups. In the square-pyramidal cation, the basal plane is formed by a meridional tridentate dipicia and a pyridyl of another bidentate dipica ligand, of which the amine group is bound at the apex. The copper ion of trans-fac-[Cu(pepica)₂](ClO₄)₂ is bound by two picolyl chelates in the equatorial plane and two elongated axial pyridyl groups. The electronic structures of these complexes are deduced based on their electronic and e.p.r. spectra. The bonding properties and the formation of the geometric isomers are elucidated.