3-(羟基-p-甲磺酰苯甲撑基)-5-氯-2-吲哚酮-1-羧酰胺类化合物的合成及生物活性研究

为了寻找高效低毒的非甾体抗炎药物, 将5-氯-2-吲哚酮与氯甲酸苯酯经酯化及水解制得1-苯氧羰基-5-氯-2-吲哚酮, 在4-N,N-二甲氨基吡啶作用下与对甲磺酰基苯甲酰氯反应, 经酸化得1-苯氧羰基-3-[羟基-(p-甲磺酰基)苯甲撑基]-5-氯-2-吲哚酮(II₁), 最后与相应的胺(氨)反应, 经盐酸中和制得未见文献报道的目标化合物II₂～II₁₅, 其结构经IR, ¹H NMR, MS和元素分析确证. 二甲苯致小鼠耳肿胀模型测试显示II₁₀, II₁₁, II₁₅具有明显的抗炎活性; 角叉菜胶致大鼠足跖肿胀模型试验结果表明, II₁₀, II₁₁抗炎活性与双氯芬酸钠和替尼达普钠相当(P＞0.05); 其中II₁₁的胃肠道副作用显著小于双氯芬酸钠(P＜0.05)和替尼达普钠(P＜0.01).     

氢化可的松与有机硝酸酯及呋咱氮氧化合物偶联物的合成、抗炎活性及安全性研究

以氢化可的松为先导物, 通过不同长度及柔度的连接基团, 分别与有机硝酸酯及呋咱氮氧化合物两类NO供体偶联, 合成了两个系列的衍生物I₁～I₇及II₁～II₈, 以期寻找到药效更强、安全性更高的新型抗炎药物. 衍生物的化学结构经MS, IR, ¹H NMR和元素分析确证. 初步抗炎活性筛选显示, 化合物I₃, II₃, II₅具有良好的抗炎活性; 进一步抗炎活性及安全性试验表明, II₅在急性、亚急性及免疫等多种炎症动物模型中活性与阳性对照物氢化可的松相当, 同时, II₅能够有效地防止骨丢失, 避免诱发高血压, 因而较之氢化可的松具有更好的安全性.     

1,2,4-三唑双席夫碱衍生物的合成及表征

氨基均三唑硫醇1a～1b与1,2-二溴乙烷缩合制得双氨基三唑硫醚2a～2b, 2a～2b与芳香醛经缩合得相应的席夫碱3a₁～3a₅与3b₁～3b₇, 收率65%～80%. 所得席夫碱类新化合物的结构均经IR, ¹H NMR, MS和元素分析确证.     

含二苯并-18-冠-6和二苯并-14-冠-4的酰胺型液晶冠醚的合成

以4-[(4-正烷氧基联苯基)-4-碳酰氧基]苯甲酸、二氨基二苯并-18-冠-6和二氨基二苯并-14-冠-4为中间体, 通过溶液缩合反应, 合成了两个系列酰胺型液晶冠醚. 并用元素分析、核磁共振、红外光谱、基质辅助激光解析电离飞行时间质谱、示差扫描量热法和偏光显微镜对其进行了表征. 随分子末端烷氧基碳原子数增加, 化合物4I, 4II, 6I和6II的熔点(T_m)和液晶态的清亮点(T_i)逐渐降低, 近晶相范围递增.     

酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性

利用柔性酚胺类配体N,N'-二甲基-N,N'-(2-羟基-4,5-二甲基苄基)乙二胺(H₂L)与Cu(Ⅱ)反应,合成了2个新的酚氧桥联多核Cu(Ⅱ)配合物[Cu₃^II(L)₂(CH₃OH)₂](ClO₄)₂(1),[Cu₃^II(L)₂(Cu^ICl₂)₂](2)。配合物1~2中,3个Cu²⁺之间通过2个酚氧桥连接,形成线性三核结构。两边的铜离子分别被配体L^2-上的N₂O₂螯合配位,轴向与甲醇分子的氧(配合物1)或[CuCl₂]^-的氯(配合物2)配位,形成四方锥配位构型。中间铜离子与两侧L^2-上的4个酚氧原子以平面四边形配位。Cu^II-O-Cu^II键角为100.14°~101.79°。对配合物1~2进行变温磁化率测量表明,铜离子之间通过酚氧桥存在强的反铁磁耦合,磁耦合常数J分别为-277(9)cm^-1(配合物1)和-299(3)cm^-1(配合物2)(基于自旋哈密顿算符Ĥ=-2J(Ŝ₁·Ŝ₂+Ŝ₂·Ŝ₃)。J值与酚氧桥桥联键角有一定相关性,即Cu-O-Cu桥联键角越大,反铁磁耦合越强。     

9-(β-D-2'-脱氧核糖基)-6-甲基嘌呤的合成

报道了9-(β-D-2'-脱氧核糖基)-6-甲基嘌呤合成的新方法. 以肌苷1为原料, 经酯化、氯化、氨解得6-氯嘌呤核苷(4), 再经过羟基保护、6-位甲基化反应及脱保护反应得到关键中间体6-甲基嘌呤核苷7, 用1,3-二氯-1,1,3,3-四异丙基二硅氧烷保护7核糖上的3,5-二羟基, 2-羟基与苯氧基硫代甲酰氯反应后得到9, 然后与氢化三正丁基锡[HSn(Bu-n)₃]还原脱氧, 最后脱保护得到目标化合物11. 产物结构经MS, ¹H NMR, 元素分析等鉴定.     

新型席夫碱大环化合物的合成

利用Mn^2＋, Ba^2＋作为模板离子, 由邻苯二胺和α,ω-二(3'-羟基-4'-甲酰苯氧基)取代烷[即1,4-二(3'-羟基-4'-甲酰苯氧基)丁烷、1,6-二(3'-羟基-4'-甲酰苯氧基)己烷、1,8-二(3'-羟基-4'-甲酰苯氧基)辛烷]反应分别合成了系列新型大环席夫碱化合物Lⁿ (n＝4, 6, 8). Mn^2＋用于L⁴合成, 并在洗涤时自动解络; L⁶和L⁸的合成以Ba^2＋模板, L⁶和L⁸的Ba^2＋配合物经与Na₂SO₄水溶液反应解络, 得到自由大环配体L⁶和L⁸. 上述新型大环席夫碱化合物采用元素分析, ¹H NMR, IR, 紫外-可见光谱和MS等进行组成和结构表征.     

“开放型蝶形”[2Fe2S]化合物光催化产氢性能与机理探究

合成并表征了两个新的具有 “开放型蝶形” 结构的[2Fe2S]化合物A和B; 并以A和B为催化剂、 藻红B钠盐 (EBS^2-) 为光敏剂、 三乙胺 (TEA) 为电子给体和质子源, 构建了一个均相光催化产氢体系. 结果表明: 体系在pH为12, 体积比为1∶1的CH₃CN/H₂O溶液中,产氢活性最高,经4 h可见光照射,最大产氢量分别为156.1 μmol (37.9 TON vs. A) 和18.4 μmol (TON 4.6 vs. B); 催化剂中含有质子捕获位点, 有利于形成产氢活性中间体H₂-Fe₂S₂(η²-H²-Fe^IIFe^I) 物种, 从而提高催化剂的产氢活性. 在当前的体系中, 还原态的 Fe^IFe⁰ 物种通过^1* EBS^2-转移到Fe^IFe^I中心上, 然后再经历一个EECC (化合物A) 或ECEC (化合物B), 形成产氢活性中间体H₂-Fe₂S₂(η²-H₂-Fe^IIFe^I)物种, 最终产生H₂分子, 并使Fe^IFe^I 物种再生.     

四种天然槲皮素-3-糖苷的合成

以芦丁为原料, 经苄基化、酸水解得到关键中间体3′,4′,7-O-三苄基槲皮素(3), 3与相应的1-溴代乙酰糖在四丁基溴化铵催化下在氯仿-0.25 mol•L^－1 K₂CO₃溶液中缩合成相应的糖苷, 脱去保护基得天然槲皮素3-糖苷类化合物 1a～1d. 其结构经IR, ¹H NMR, MS及元素分析确证.     

β-D-葡萄糖基硫脲合成及生物活性研究

从1-溴-2,3,4,6-四乙酰化-β-D-吡喃葡萄糖I出发, 经异硫氰酸酯化反应, 合成了2,3,4,6-四乙酰化-β-D-吡喃糖基硫脲化合物IV, 再经脱乙酰化得到V. 将乙酰化糖基异硫氰酸酯的合成从文献的60%提高到80%. 所得化合物经元素分析, IR, MS, ¹H NMR和 ¹³C NMR谱学分析确定了结构, 并对产物进行了初步的除草活性测试.     

Protolytic properties and complexation with copper(II) ions of some azo derivatives of β-arylaminopropionic acids

The azo coupling reaction of N-(2-carboxyethyl)anthranilic acid and N,N,N′,N′-tetrabis(2-carboxyethyl)-1,3-phenylenediamine with diazosulfanilic acid yielded the complexones sodium 4-N-(2-carboxyethyl)amino-5-carboxyazobenzene-4′-sulfonate (I) and 2,4-N,N,N′,N′-tetrabis(2-carboxyethyl)diaminoazobenzene-4′-sulfonic acid (II), respectively. The acidity constants of I and II (20°C, μ = 0.1M KCl) were determined to be as follows: for I, pK ₀₀ = 1.29 ± 0.13, pK ₀ = 2.92 ± 0.07, pK ₁ = 3.92 ± 0.05, pK ₂ = 5.16 ± 0.03; for II, pK ₀₀ = 2.35 ± 0.06, pK ₀ = 2.81 ± 0.09, pK ₁ = 3.21 ± 0.11, pK ₂ = 3.81 ± 0.09, pK ₃ = 4.34 ± 0.04, pK ₄ = 5.03 ± 0.06, pK ₅ = 6.67 ± 0.07. The electronic absorption spectra of I and II were measured, and acid-base equilibrium scheme for I and II in aqueous solutions were suggested. The complexation constants of I and II with copper(II) ions were determined to be logK _CuQ^I= 5.47 ± 0.06 and logK _CuQ^II= 5.72 ± 0.13 (20°C, μ = 0.1 M KCl).     

Synthesis,characterization and antimicrobial activity of cobalt(II), nickel(II)and copper(II) complexes with new asymmetrical Schiff base ligands derived from 7-formyanil-substituted diamine-sulphoxine and acetylacetone

Asymmetric 7-formyanil-substituted-imino-4-(4-methyl-2-butanone)-8-hydroxyquinoline-5-sulphonic acid (Schiff bases), react with Co^II, Ni^II and Cu^II ions to give 1:2, 1:1 and 2:1 complexes as established by conductometric titrations in 1:1 DMF:H₂O. The complexes were investigated by elemental analyses, molecular weight determinations, molar conductance, magnetic moments, thermal analysis, i.r., u.v.–vis. and e.s.r. spectra. The complexes have an octahedral crystal structure and general formula [ML·(OH₂)₂], where M^II = Co, Ni and Cu, and L = Na[7—X—HL], (—X— = (CH₂)₂, (CH₂)₃, p-C₆H₄, o-C₆H₄). Antimicrobial activity of these new ligands and their transition metal complexes has been screened in vitro on common fungi and bacteria.     

Bridging chlorides and hydroxides: syntheses and crystal structures of binuclear and tetranuclear NiII complexes derived from a reduced Schiff-base ligand 2-(2-pyridylmethylamino)ethanesulfonic acid

Two complexes, [Ni(pmt)(Cl)] (1) and [Ni₄(pmt)₄(OH)₄]·8H₂O (2) [Hpmt = 2-(2-pyridylmethylamino)ethanesulfonic acid], were synthesized by different experimental methods in methanol-water mixed solution. Compound 1 crystallizes in triclinic, space group P?1 with unit cell parameters: a = 8.315(2) Å, b = 8.383(2) Å, c = 9.128(2) Å, α = 103.654(2)°, β = 98.125(2)°, γ = 113.154(2)°, V = 548.6(2) ų, Z = 2. A pair of chlorides is μ ₂-bridges linking two Ni^II atoms in forming binuclear complex 1. The coordination environment at Ni^II is distorted square-pyramidal geometry. Compound (2) belongs to monoclinic, space group C2/c, with a = 16.5168(15) Å, b = 18.3718(17) Å, c = 17.5473(16) Å, α = γ = 90°, β = 93.3820(10)°, V = 5315.3(8) ų, Z = 4. Four hydroxides are μ ₃-bridges joining four Ni^II atoms to generate a cubic framework as a tetranuclear complex. The configuration at each Ni^II is distorted octahedral. Both π–π stacking of pyridine rings and intermolecular hydrogen bonds stabilize the solid state structures for 1 and 2.     

通过氢键构筑的含3-硝基邻苯二甲酸的层状超分子化合物

合成了含大量氢键的层状超分子化合物[C₄H₁₂N₂](HL)₂ (I)和[YL(HL)(H₂O)₃]₂•2H₂O (II) (H₂L＝O₂NC₆H₃- (CO₂H)₂, 3-硝基邻苯二甲酸), 并通过元素分析、红外分析和单晶X衍射表征了组成与结构. 化合物I为双质子化哌嗪阳离子和3-硝基邻苯二甲酸氢根阴离子组成的加合物, 阴离子之间靠强烈的O—H…O氢键形成无限链状结构, 同时阴离子链通过N—H…O氢键与阳离子扩展成网状结构, 相邻的网状结构再由分子间弱作用力构筑成层状超分子. 化合物II则是在双核稀土配合物结构单元通过O—H…O氢键构成的网状结构基础上再进一步由层间弱作用力构筑成的层状超分子化合物. 化合物II的网格结构中, 菱形单元空隙里填充的两个结晶水通过氢键将结点上的双核单元更牢固地结合在一起. 化合物I为单斜晶系, P2₁/c空间群, a＝1.3176(3) nm, b＝1.1096(2) nm, c＝0.75950(15) nm, b＝97.14(3)°, V＝1.1017(4) nm³, Z＝4, μ＝0.129 mm^－1, D_c＝1.533 Mg/m³. 化合物II为三斜晶系, P-1空间群, a＝0.81262(16) nm, b＝0.86942(18) nm, c＝1.5011(3) nm, α＝99.84(3)°, β＝91.26(3)°, γ＝104.55(3)°, V＝1.0091(4) nm³, Z＝1, μ＝2.983 mm^－1, D_c＝1.910 Mg/m³.     

3-芳基-1,2,3,4-噁三唑-5-亚胺与阿司匹林偶联物的合成和抗血栓活性研究

取代苯胺经重氮化、还原得苯肼盐酸盐, 与硫氰酸钾作用得苯基取代的氨基硫脲, 再在亚硝酸异戊酯、盐酸的作用下环合、成盐, 加碱中和后生成3-芳基-1,2,3,4-噁三唑-5-亚胺, 最后与乙酰水杨酰氯反应得目标物6a～6l, 其结构经MS, IR, ¹H NMR和元素分析确证. 体外血小板聚集试验和小鼠肺血栓生成试验结果表明, 部分目标物在体内、外均显示出较好的抗血栓活性, 值得深入进行研究.     

Synthesis and Crystal Structure of Acid Phosphites RbH2PO3, CsH2PO3, and TlH2PO3

The reaction of Rb, Cs, or Tl carbonates with a solution of phosphorous acid gave crystalline acid phosphites RbH₂PO₃(I), CsH₂PO₃(II), and TlH₂PO₃(III). The crystal structures of the compounds were studied by a single-crystal X-ray diffraction analysis at 150 K: I, monoclinic system, a= 7.530(2) Å, b= 8.634(2) Å, c= 12.426(2) Å, = 102.46(3)°, V= 788.8(3) ų, Z= 8, space group P2₁/c, R ₁= 0.0409; II, monoclinic system, a= 7.930(2) Å, b= 8.929(2) Å, c= 13.163(3) Å, = 104.84(3)°, V= 900.9(4) ų, Z= 8, space group P2₁/c, R ₁= 0.0239; III, orthorhombic system, a= 6.603(1) Å, b= 6.785(1) Å, c= 8.836(2) Å, V= 395.9(1) ų, Z= 4, space group Pna2₁, R ₁= 0.0350. The PHO₃tretrahedra in structures I–IIIare joined via hydrogen bonds into infinite zigzag-like chains [HPHO₃] ^n– _n, which form layers alternating with layers of metal cations. The layers of anionic chains are wavelike in Iand IIand planar in III. Apparently, IIIis not isostructural to Ior IIdue to the fact that Tl(I) has a stereochemically active pair of electrons.     

Regio-and Stereo-selective Synthesis of Peracetylated Carbohydrate Esters of Aromatic Fatty Acid Using p-Toluenesulfonic Acid as Catalyst

This paper describes an efficient synthesis of carbohydrate fatty acid esters based on a highly stereo‐ and regio‐selective esterification. The suitably protected glycosyl was esterified with stearic acid to give mainly the β‐anomer in good yield using p‐toluenesulfonic acid as catalyst. The structures of these compounds were fully confirmed by ¹H, ¹³C NMR, mass spectra and HRMS.     

Metal chelates with some cellulose derivatives; part IV. Structural chemistry of HEC complexes

Reactions of hydroxyethyl cellulose (HEC) with Cr ^III, Ni^II, Co^II, or Cu^II chlorides in aqueous medium yielded complexes with formulae [M(HEC)Cl _m .n H ₂O], wherem =1 or 2 and n=2 or 3. HEC acted as a uninegatively charged bidentate ligand in the case of Cr^III and Ni^II, and as a neutral ligand in the case of Co^II and Cu^II complexes. The spectra showed that the binding sites in Cr^III and Ni^II complexes were the ether oxygen between two ethoxyl groups and the oxygen of the hydroxyl group; while in the Co^II and Cu^II complexes the binding sites were the oxygen of ethoxyl groups and the primary alcoholic O atom of glucopyranose rings. These complexes would most likely exhibit octahedral geometry with Cr^III, Ni^II, and Co^II, but square planar configuration in the case of the Cu^II complex. The ligand parameters of the Cr^III, Ni^II, and Co^II metal chelates were calculated in different solvents and at different temperatures. The thermal stability of the above complexes was investigated and the overall thermodynamics functions G⁰, H⁰, and S⁰, associated with complex formation, were estimated.