Synthesis and properties of oligomers containing substituted bithiazole rings

A series of novel polyimide and poly(Schiff base) oligomers containing substituted bithiazole rings were designed and synthesized, for the first time, by polycondensation of 5,5^′-dimethyl-2,2^′- diamino-4,4^′-bithiazole (MDABT) with dianhydrides (pyromellitic dianhydride, 3,3^′-4,4^′-benzophenone tetracarboxylic dianhydride and bis (3,4-dicarboxyphenyl) ether dianhydride), and dialdehydes (oxalic aldehyde, isophthalaldehyde and terephthalaldehyde). The structure of the oligomers was determined by IR and ¹H NMR spectroscopy, and elemental analysis. The oligomers showed good thermal stability. The Fe²⁺ complex of poly(Schiff base), synthesized from MDABT with oxalic aldehyde (PMTOA), was prepared with 13.7% Fe content and found to be a ferromagnet at low temperature.     

PREPARATION AND MAGNETIC PROPERTIES OF POLY(SCHIFF BASE) COMPLEXES CONTAINING PHENANTHROLINE UNITS

 Two poly(Schiff base)s (PDBT and PDPE) were synthesized by polycondensation of 1,10-phenanthroline-5,6-dione (PD) with 2,2′-diamino-4,4′-bithiazole (DABT) and 4,4′-diaminodiphenyl ether (DAPE), respectively. The structures of the polymers were determined by FTIR and element analysis. The metal (Fe²⁺, Ni²⁺) complexes were prepared from the polymers with FeSO₄ or NiSO₄, and the metal contents of the complexes were measured by complexometric titration. The magnetic behaviors of the complexes were examined as a function of magnetic field strength at 4 K and as a function of temperature (4-300 K) at a magnetic field strength of 2.4 ×106 A/m. The results show that the relative saturation magnetization of the PDBT complexes is higher than that of the corresponding PDPE complexes, and PDBT-Ni²⁺ and PDPE-Ni²⁺ are soft ferromagnets, while PDBT-Fe²⁺ and PDPE-Fe²⁺ exhibit the features of antiferromagnet.     

Lead(II) complexes of 2,2′-diamino-4,4′-bithiazole (DABTZ) including crystal structure of a novel 1D chain polymer, [PB(DABTZ)(μ-SCN)(μ-NO3)] n

Three new 2,2′-diamino-4,4′-bithiazole (DABTZ) lead(II) complexes were synthesized and characterized by elemental analyses, IR-, ¹H-NMR-, and ¹³C-NMR-spectroscopy. The single crystal X-ray structural analysis of [Pb(DABTZ)(μ-SCN)(μ-NO₃)] _n shows the complex to be a 1D chain polymer as a result of sequential thiocyanate and nitrate bridging. The Pb atoms are seven-coordinated by two nitrogen atoms of the 2,2′-diamino-4,4′-bithiazole, three nitrate and two thiocyanate ligands. The arrangement of the 2,2′-diamino-4,4′-bithiazole, nitrate and thiocyanate ligands does not suggest a gap in the coordination around the Pb^II ion, caused by a stereo-active lone pair of electrons on lead(II) where the coordination around the lead atoms is the less common holodirected.     

Structural and solution studies of new cadmium(II) complexes with 2,2′-diamino-4,4′-bithiazole

Two new Cd(II) complexes, [Cd(DABT)(CH₃COO)₂] (1) and [Cd(DABT)(NO₃)₂] (2), DABT = 2,2′-diamino-4,4′-bithiazole, have been synthesized and characterized by single crystal X-ray crystallography. In 1, each cadmium is chelated by two nitrogens of one DABT and four oxygens of acetate, whereas 2 is a dinuclear complex and there are two Cd's with eight and six coordination: Cd₁O₆N₂ and Cd₂O₄N₂ units. The counter ion effect of the complex formation reaction between cadmium(II) nitrate and acetate with DABT has been studied by spectroscopy. The formation constants of the 1 : 1 and 1 : 2 (metal ion to ligand) complexes were evaluated by computer fitting of the absorbance–mole ratio data.     

2,2’-二甲基-4,4’-联噻唑与CHCl3分子间相互作用的理论研究

采用量子化学从头算理论在MP2/6-31G(d,p)水平上对2,2’-二甲基-4,4’-联噻唑顺反异构体, trans-2,2’-二甲基-4,4’-联噻唑-CHCl3 (I), cis-2,2’-二甲基-4,4’-联噻唑-CHCl3 (II)形成的1∶1氢键复合物进行计算研究. 结果表明, 2,2’-二甲基-4,4’-联噻唑在气相条件下, 反式构象比顺式构象稳定. 氯仿与2,2’-二甲基-4,4’-联噻唑形成的复合物存在较强的氢键, 表现为氮原子的孤对电子与氯仿分子中C—H反键σ轨道的相互作用, 另外形成C—H…Cl弱相互作用, 氢键作用使2,2’-二甲基-4,4’-联噻唑的顺式结构在氯仿溶剂比反式结构更稳定.     

芳杂环聚西佛碱Fe~(2+)配合物的合成及磁性能

以 2 ,2′ 二氨基 4 ,4′ 联噻唑 (DABT) ,2 ,6 二乙酰基吡啶 (DAP)及苯二甲醛为原料合成了三个新型结构的芳杂环聚西佛碱 (PBTAP ,PBTMP ,PBTPP) ,并制备了其相应的Fe2 + 配合物 .利用FTIR确定了聚合物及其配合物的结构 ,借助多功能材料物理特性测量系统 (PPMS :PhysicalPropertyMeasurementSystem)测定配合物的磁性能 ,测试结果表明这三个聚合物的Fe2 + 配合物都是有机软磁体 ,具有相对较高的磁饱和强度 (Ms) ,其中PBTAP Fe2 + 的磁饱和强度为 6 2emu g ,顺磁居里温度 (Tp)达 88K ,且具有S型的磁滞回线 ,此结果表明此配合物在低温下是有机软铁磁体 .     

Synthesis and magnetic properties of novel poly(Schiff base)‐Fe2+ complexes

Three polymer‐Fe²⁺ complexes were synthesized from Fe²⁺ and poly(Schiff base)s. The poly(Schiff base)s were prepared from 2,2′‐diamino‐4,4′‐bithiazole (DABT) with phthalaldehyde, 5,5′‐methylenebis(salicylaldehyde) (MBSA) and terephthalaldehyde, respectively, and characterized by IR, XPS, NMR and ESR spectroscopy. The magnetic behavior of these polymer‐Fe²⁺ complexes was examined as a function of magnetic field strength and temperature (5–300 K), respectively. The hysteresis loops were also studied. Based on these results, several novel ferromagnets were obtained.     

Synthesis, characterization, antitumor activity of nickel(Ⅱ) and cobalt (Ⅱ) complexes of 2,2''''-diamino-4,4''''-bithiazole and their interaction with dGMP

New complexes,of bis(2,2'-diamino-4,4'-bithiazole)sulfate nickel(Ⅱ) and bis(2,2'-diami-no-4,4'-bithiazole)sulfate cobalt(Ⅱ),have been prepared.The complexes were characterized by infrared and UV-Vis spectroscopy,1H NMR,elemental analyses and molar conductivity.The effect of these complexes on the DNA synthesis of sarcoma 180 cells has been studied by the technique of isotopic liquid scintillation.The results indicated that complexes show ability to inhibit DNA synthesis of the tumor cells.In order to provide a molecular basis for understanding the biological effects,the probe,[trana-en2Os(η2-H2)](CF3SO3)2 (en,ethylenediamine) as a monitor was first used to explore interaction of the complexes with 2'-deoxyguanosine-5'-monophosphate (dGMP).     

Spectroscopic, thermal and structural studies of cocrystal of 2,2′-diamino-4,4′-bis(1,3-thiazole) with 4,4′-bipyridine, 1,2-bis(4-pyridyl)ethylene and 1,3-bis(4-pyridyl)propane

Three new cocrystals based upon 2,2′-diamino-4,4′-bis(1,3-thiazole) (DABTZ) with 4,4′-bipyridine (4,4′-bipy), 1,2-bis(4-pyridyl)ethylene (bpe) and 1,3-bis(4-pyridyl)propane (bpp): [(DABTZ) (4,4′-bipy)], [(DABTZ) (bpe)] and [(DABTZ) (bpp)] have been synthesized and characterized by elemental analysis, IR-, ¹H NMR-, ¹³C NMR spectroscopy and studied by thermal and X-ray crystallography. Self-assembly of these compounds in the solid state is likely caused by both hydrogen bonding, and π-π stacking.     

PREPARATION AND MAGNETIC PROPERTIES OF POLY(SCHIFF BASE) COMPLEXES CONTAINING PHENANTHROLINE UNITS

Two poly(Schiff base)s (PDBT and PDPE) were synthesized by polycondensation of 1,10-phenanthroline-5,6- dione (PD) with 2,2′-diamino-4,4′-bithiazole (DABT) and 4,4′-diaminodiphenyl ether (DAPE),respectively.The structures of the polymers were determined by FTIR and element analysis.The metal (Fe~(2+),Ni~(2+)) complexes were prepared from the polymers with FeSO_4 or NiSO_4,and the metal contents of the complexes were measured by complexometric titration.The magnetic behaviors of the complexes were examine...     

Synthesis,characterization and dyeing performance of new bisazo–bisazomethine disperse dyes

New bisazo–bisazomethine disperse dyes were prepared by the coupling of diazotized solutions of various aromatic amines with 2,2′-{methylenebis[4,1-phenylenenitrilomethylylidene]}diphenol (Schiff base). Schiff base (SB) was prepared by the condensation of 2-hydroxybenzaldehyde with 4,4′-diaminodiphenylmethane (DDM). The resultant dyes were characterized by elemental analysis, IR and ¹H NMR spectral studies. The UV–visible absorption spectral data were investigated in dimethylformamide (DMF) and are discussed in terms of structure property relationship. The dyes when applied on polyester fabric, gave golden yellow to reddish brown shades having fairly good to good light fastness, very good to excellent washing, perspiration and sublimation fastness and good to very good rubbing fastness properties.     

Bithiazole-bridged polysilsesquioxane and its metal complexes: synthesis and magnetic properties

A novel alkoxysilylated derivative based on 2,2′-diamino-4,4′-bithiazole (DABTH) was firstly synthesized. The corresponding polysilsesquioxane (PBSIBTH) and its metal complexes (PBSIBTH-Eu³⁺, PBSIBTH-Tb³⁺ and PBSIBTH-Ni²⁺) were also obtained via sol–gel method, respectively. The morphology of their xerogels was investigated by scanning electron microscopy means. The magnetic measurements of these polymer complexes show all obtained solid materials feature soft ferromagnet properties at low temperature. The metal ions in polymer complexes have a significant influence on both microstructure and magnetic properties.     

2,4-二氨基-6-苯基-1,3,5-三嗪聚席夫碱Fe~(2+)配合物的合成及性能研究

以 2 ,4 二氨基 6 苯基 1,3,5 三嗪 ,2 ,2′ 二氨基 4 ,4′联噻唑 (DABT) ,苯二甲醛及乙二醛等为原料 ,合成了 6个新型结构的含芳杂环聚席夫碱 (DAPIPA ,DAPTPA ,DAPA ,DAPGPBTGZ ,PBTPZ) ,并制备了 2个Fe2 +配合物 (PBTGZ Fe2 + ,PBTPZ Fe2 + ) .利用FTIR和1 H NMR对聚合物的结构进行了表征 ,通过对其中 3个聚席夫碱的热失重分析 ,表明聚合物具有良好的耐热性能 ,借助多功能材料物理特性测试系统 (PPMS :physicalpropertymeasurementsystem)测定配合物的磁性能 ,测定结果表明这些配合物具有相对较高的磁饱和强度 (σs) ,且有典型的S型磁滞回线 ,表明配合物是有机软铁磁体 .     

Synthesis and magnetic properties of complexes of a conjugated hyperbranched polymer containing bithiazole rings

A novel conjugated hyperbranched polymer containing bithiazole rings（PBTADB） was synthesized by polycondensation of 1,3,5-benzenetricarboxaldehyde and 2,2’-diamino-4,4’-bithiazole（DABT）.The structure of the hyperbranched polymer was confirmed by FT-IR and ¹H-NMR.PBTADB dissolved in organic polar solvents such as DMSO and NMP.Bithiazole rings were introduced to provide bidentate N-donor sites for binding metal ions.The metal complexes were prepared by chelation of the polymer with Co²⁺ and Sm³⁺.The magnetic behavior of coordination compounds was measured as a function of magnetic field strength（0-4.8×10⁶ A/m） at 5 K and as a function of temperature（5-300 K） at magnetic field strength of 2.4×10⁶ A/m.The magnetic hysteresis loops of PBTADB-Sm³⁺and PBTADB-Co²⁺showed the typical ’S’ shape at 5 K with the Curie-Weiss temperature T_θ=96 K and 41 K respectively.The results show that they exhibit properties of soft ferromagnetic materials.     

Synthesis and characterizations of 3,3′-bis(diphenylphosphinoamine)-2,2′-bipyridine and 3,3′-bis(diphenylphosphinite)-2,2′-bipyridine and their chalcogenides

New bis(phosphinoamine) and bis(phosphinite) derivatives of 2,2′-bipyridine were prepared through a single step reaction of 3,3′-diamino-2,2′-bipyridine or 3,3′-dihydroxy-2,2′-bipyridine with diphenylchlorophosphine, respectively. Their P = E chalcogenides (E = O, S, Se) were also prepared. All the new compounds were characterized by elemental analysis, IR and NMR spectroscopies. The molecular structure of 3,3′-bis(diphenylthiophosphinite)-2,2′-bipyridine was elucidated by single-crystal X-ray crystallography.     

Improved synthesis of 4,4′-diamino-2,2′-bipyridine from 4,4′-dinitro-2,2′-bipyridine-N,N′-dioxide

A superior synthetic route to 4,4′-diamino-2,2′-bipyridine has been developed. This procedure compares favorably with existing methods, producing 4 times the yield previously reported. In addition, mild reaction conditions are utilized, allowing a considerably more efficient production, and subsequent purification, of the diamino complex.     

Synthesis of substituted 1,1′-diaminoferrocenes from cyclo-2-pentene imines

Condensation of anilines and primary aliphatic amines with 3,4-diphenylcyclo-2-pentenone leads to the corresponding diphenylcyclopentene imines in good yields of 72-90%. Deprotonation of these aminocyclopentadiene tautomers and reaction with FeCl₂ leads to the synthesis of the respective 1,1′-diamino-3,3′,4,4′-tetraphenylferrocenes. Yields increase from 33% to 65% with a decrease in the steric bulk of the amine substituent. The observation that a successful conversion requires two equivalents of base is conceived on the basis of the discussed reaction mechanism. The molecular structure of 1,1′-dianilino-3,3′,4,4′-tetraphenylferrocene (3a), which was determined by single crystal X-ray analysis reveals a trans coordination of the two amine moieties with respect to the central Cp-Fe-Cp axis of the ferrocenyl backbone.     

Design of postmetallocene Schiff base-like catalytic systems for polymerization of olefins: XII. Synthesis of tetradentate bis-salicylaldehyde imine ligands

Reactions of salicylaldehyde, 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′,5,5′-tetramethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclopentyl-3,3′-dimethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclohexyl-3,3′-dimethyldiphenylmethane, bis(4-aminophenyl) sulfone, o,o′- and p,p′-diaminodiphenyl ethers, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 4,4″-diamino-p-terphenyl gave a series of the corresponding Schiff bases which can be used as tetradentate ligands for the synthesis of titanium and zirconium complexes.     

含双噻唑基聚合物的合成及电流变性能研究

采用2，2’-二氨基-4，4’-双噻唑与联苯胺合成一种含有双噻唑基的共轭聚合物，通过红外、扫描电镜、热重分析等测试了该物质的结构及热稳定性等，并通过将聚合物分别分散在硅油和溴代二苯甲烷中制备电流变体，测试其电流变性能。结果表明：含双噻唑基的共轭聚合物作为电流变体的分散相表现出了良好的电流变性能，同时发现分散相和分散介质的密度相近时有利于电流变性能的提高。     

A new class of aromatic polybenzoxazoles containing ortho-phenylenedioxy groups

A series of poly(o-hydroxy amide)s having both ether and ortho-catenated phenylene unit in the main chain were synthesized via the low-temperature solution polycondensation of 4,4^′-(1,2-phenylenedioxy)dibenzoyl chloride and 4,4^′-(4-tert-butyl-1,2-phenylenedioxy)dibenzoyl chloride with three bis(o-aminophenol)s including 4,4^′-diamino-3,3^′-dihydroxybiphenyl, 3,3^′-diamino-4,4^′-dihydroxybiphenyl, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. The poly(o-hydroxy amide)s exhibited inherent viscosities in the range of 0.23-0.96 dl/g. Most of the poly(o-hydroxy amide)s were soluble in polar organic solvents such as N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP) and could afford flexible and tough films by solution casting. Subsequent thermal cyclodehydration of the poly(o-hydroxy amide)s afforded polybenzoxazoles. However, the polybenzoxazoles were organic-insoluble except for those with the hexafluoroisopropylidene group. The polybenzoxazoles exhibited glass-transition temperatures (T_g) in the range of 200-232 °C by DSC and softening temperatures (T_s) of 250-256 °C by thermomechanical analysis. Thermogravimetric analyses indicated that most polybenzoxazoles were stable up to 500 °C in air or nitrogen. The 10% weight loss temperatures were recorded in the ranges of 546-606 °C in air and 574-631 °C in nitrogen.