Crown ether molecular complexes with urea and thiourea

Crystalline complexes of urea and thiourea with crown ethers, have been prepared, viz., 18-crown-6 (18C6), benzo-18-crown-6 (B18C6), dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DC 18C6) and dibenzo-24-crown-8 (DB24C8). While the complexes of the large ring size crown ether, DB24C8, have high ether to (thio)urea ratios, the stoichiometry of the others lies between one molecule of crown ether and from one to six molecules of (thio)urea. An IR spectral study of the urea and thiourea complexes showed that the behavior of thiourea in these complexes is clearly different from that of urea, indicating the role of sulphur in the interaction of thiourea with crown ethers. The urea and thiourea complexes were classified according to their stoichiometries and their IR spectral behavior into three classes for which credible structures were proposed.     

用硫脲分子表面修饰的CdS纳米粒子的合成和表征

报道了用硫脲分子进行表面化学修饰的CdS纳米粒子的合成方法,并引入了AOT(磺基琥珀酸双-2-乙基己基酯钠盐)作为平衡反离子,进一步对CdS表面作了修饰,增加了CdS纳米粒子在有机溶剂中的稳定性和可分散性。我们还探讨了温度、浓度、pH等因素对合成的影响,并通过TEM、XRD、FT-IR等手段对产物结构进行了表征。所得微粒粒径为5 nm左右,呈球形,硫脲分子与CdS纳米粒子富Cd²⁺表面通过形成Cd-S配位键而修饰在粒子表面。这种表面修饰的CdS纳米粒子将在非线性光学及自组装方面具有优     

醋酸锰催化合成萘并噻唑衍生物研究型综合实验

设计了“醋酸锰（Ⅲ）催化合成2-邻氯苯甲酰氨基萘并[1,2-d]噻唑”研究型综合化学实验,以自制的醋酸锰（Ⅲ）为催化剂,催化氧化1-萘基-3-邻氯苯甲酰基硫脲合成2-邻氯苯甲酰氨基萘并[1,2-d]噻唑。通过该实验项目的教学,可使学生掌握醋酸锰（Ⅲ）、1-萘基-3-邻氯苯甲酰基硫脲和2-邻氯苯甲酰氨基萘并[1,2-d]噻唑的合成方法,掌握有机化合物结构表征的方法,可以培养学生的实践动手能力、科研创新能力以及综合运用知识的能力。该实验项目集无机合成实验、有机合成实验和仪器分析实验于一体,具有较强的可操作性和实用性,可作为基础化学研究型综合化学实验或开放性实验开设。     

A novel heterogeneous nanocatalyst: 2‐Methoxy‐1‐phenylethanone functionalized MCM‐41 supported Cu(II) complex for C‐S coupling of aryl halides with thiourea

An environmentally friendly copper‐based catalyst supported on 2‐Methoxy‐1‐phenylethanone functionalized MCM‐41 was prepared and characterized by FT‐IR, FE‐SEM, TEM, XRD, EDX, BET and ICP techniques. The catalyst was applied for the C?S cross‐coupling reaction of aryl halides with thiourea. Corresponding products were produced in good yields in aerobic conditions. The catalyst could be recovered and recycled for several times.     

Synthesis,characterization, crystal structure,and antimicrobial studies of novel thiourea derivative ligands and their platinum complexes

N,N-Di-R-N′-(4-chlorobenzoyl)thiourea (Di-R: diethyl, di-n-propyl, di-n-butyl and diphenyl) ligands (HL^1–4) and their Pt(II) complexes (cis-[Pt(L^1–4-S,O)₂]) have been synthesized and structurally characterized by elemental analyses, FT-IR and NMR spectroscopy. HL² ligand and cis-[Pt(L⁴-S,O)₂] metal complex have been also characterized by a single-crystal X-ray diffraction study. HL², C₁₄H₁₉ClN₂OS, crystallizes in the monoclinic space group P2₁/n (no. 14), with Z = 4, and unit cell parameters, a = 11.1405(16) Å, b = 9.7015(12) Å, c = 14.790(2) Å, β = 106.547(7)°. The cis-[Pt(L⁴-S,O)₂], C₄₀H₂₈Cl₂N₄O₂PtS₂: triclinic, space group P-1 (no. 2), a = 8.9919(3) Å, b = 14.7159(6) Å, c = 15.7954(6) Å, α = 113.9317(18)°, β = 97.4490(18)°, and γ = 105.0492(16)°. Single crystal analysis of complex, cis-[Pt(L^1–4-S,O)₂], revealed that a square planar coordination geometry is formed around the platinum atom by two sulfur and two oxygen atoms of the related ligands, which are in a cis configuration. In addition, the thiourea derivative ligands and their complexes were evaluated for both their in-vitro antibacterial and antifungal activity. The results have been reported, explained, and compared with fluconazole and ampicillin, used as reference drugs.     

Synthesis,characterization, speciation and biological studies on metal chelates of 1-benzoyl(1,2,4-triazol-3-yl)thiourea

Proton-ligand association constants of 1-benzoyl(1,2,4-triazol-3-yl)thiourea (BTTU) and its complex formation constants with some bivalent metal ions Ni(II), Co(II), Mn(II), Zn(II), and Cu(II), have been determined potentiometrically in 50% EtOH–H₂O and 0.1 M NaNO₃. The complexes formed in solution have a stoichiometry of 1:1 and 1:2 [M:L], where M represents the metal ion and L the BTTU ligand. The corresponding thermodynamic parameters are derived and discussed. The complexes are stabilized by enthalpy changes and the results suggest that complexation is an enthalpy-driven process. The effects of metal ion, ionic radius, electronegativity, and nature of ligand on the formation constants are discussed. The formation constants of the complexes with 3d transition metals follow the order Mn²⁺ < Co²⁺ < Ni²⁺ < Cu²⁺ > Zn²⁺. The metal complexes were synthesized and characterized by elemental analyses, conductance, IR, ¹H NMR, and magnetic measurements. The low magnetic moment of 0.11 BM for the Cu(II) complex is suggestive of dimerization through Cu–Cu interaction. The concentration distribution diagrams of the complexes were evaluated. The ligands and their metal complexes have been screened in vitro against some bacteria and fungi.     

Multicenter ligand transformations of thioureas on ruthenium clusters

The reaction of trirutheniumdodecacarbonyl with various thioureas was found to give, depending upon the substituents and the reaction conditions, a large variety of tri-, tetra-, penta-, and hexanuclear ruthenium clusters. The ligand systems observed in the products are derived from the thioureas employed; the fragmentation of the thiourea molecules involve N-H, C-S, C-H, and C-N activation processes.     

新型间苯二酚杯芳烃硫脲衍生物对阴离子的识别

通过间苯二酚杯芳烃连续三步反应, 以较高产率合成了分子中连有8个和12个硫脲端基的间苯二酚杯芳烃的酰胺衍生物. 用紫外可见光谱法研究了两个代表性化合物4,6,10,12,16,18,22,24-八[6-(苯基硫脲基)-己氨甲酰基甲氧基]-2,8,14,20-四苯基杯[4]间苯二酚芳烃(THBC)和4,6,10,12,16,18,22,24-八[2-(苯基硫脲基)-1-甲基乙基-1-氨甲酰基甲氧基]-2,8,14,20-四苯基杯[4]间苯二酚芳烃(TPBC), 对各种阴离子(AcO^－, H₂PO₄^－, HSO₄^－, H₂PO₄^2－, C₁₂H₂₅-C₆H₄-SO₃^－, Cr₂O₇^2－, B₄O₇^2－, Cl^－, Br^－)的识别性能, 结果表明它们对AcO^－, H₂PO₄^－, HSO₄^－等阴离子有较好的配位作用, 能形成1∶3的配合物.     

L-鼠李糖基(氨基)硫脲类化合物的合成

以L-鼠李糖为起始原料, 制备1-溴-2,3,4-三-O-乙酰基-β-L-吡喃型鼠李糖, 然后在甲苯中与Pb(SCN)₂作用, 得到中间体2,3,4-三-O-乙酰基-α-L-吡喃型鼠李糖基异硫氰酸酯(1). 利用2,3,4-三-O-乙酰基-α-L-吡喃型鼠李糖基异硫氰酸酯易发生亲核加成的性质, 在不同溶剂中, 与取代的苯并噻唑胺(2a～2f)、取代的苯并噻唑肼(2g～2l)、氧化和非氧化的哒嗪酮甲酰肼(2m, 2n)以及取代的嘧啶胺(2o, 2p)反应, 合成了16种新的(氨基)硫脲类化合物3a～3p. 所有化合物的结构均经IR, ¹H NMR, LC-MS和元素分析确证, 并对它们的生物活性做了初步测试.