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。     

α,β-聚（N-2-羟乙基）-L-天冬酰胺的合成及对Pb2+和Cu2+螯合性能的研究

以天冬氨酸热缩聚得到的聚琥珀酰亚胺(PSI)为原料,与乙醇胺通过氨解开环反应,合成了聚天冬氨酸的接枝衍生物α,β-聚(N-2-羟乙基)-L-天冬酰胺(PHEA)。用红外光谱表征了产物的结构;用凝胶色谱测定了分子量分布。研究了PHEA用量、pH值和金属离子初始浓度等对Pb2+和Cu2+去除率的影响,在pH=5.0时,Pb2+的最大去除率为92.48%;在pH=4.5时,Cu2+的最大去除率为89.34%。Pb2+和Cu2+最大静态螯合量分别为25.64mg/g和17.68mg/g。通过XPS分析得知,PHEA与Pb2+螯合时,氮原子和氧原子参与了反应;与Cu2+螯合时,主要是氧原子参与反应。     

旋光聚[乙烯-alt-R-N-(1-苯乙基)马来酰胺酸]的合成及静电自组装

以聚(乙烯-alt-马来酸酐)为原料,通过与R-(+)-α-苯乙胺的酰胺化反应,合成了一种新型的旋光聚电解质聚[乙烯-alt-R-N-(1-苯乙基)马来酰胺酸],利用红外吸收光谱、紫外吸收光谱、核磁共振氢谱和旋光度数据对其结构进行表征.聚[乙烯-alt-R-N-(1-苯乙基)马来酰胺酸]与聚二甲基二烯丙基氯化铵(PDDA)逐层静电自组装过程的紫外跟踪测试结果表明,带相反电荷的聚电解质间能够形成稳定增长的自组装膜,多层膜组装量随双层数指数增大.     

汞(Ⅱ)在螯合树脂聚[对乙烯苄基-(2-羟乙基)硫醚]上的吸附机理

研究了Hg2+在自合成的新型含硫螯合树脂-聚[对乙烯苄基-(2-羟乙基)硫醚](PSME)上的吸附机理.静态吸附结果表明吸附属于液膜扩散控制机理;树脂对Hg2+的等温吸附过程可以用Freundlich方程描述;在吸附过程中存在着明显的氧化还原现象.在较低浓度下,Hg2+主要被还原成Hg2+2和Hg0;而在较高浓度下Hg2+则主要被还原成Hg2+2.在两种情况下,-S-均被氧化成-SO2-键.     

正电子发射显像剂O-(2-[18F]氟乙基)-L-酪氨酸的新型前体的合成

设计合成了5种新型正电子发射断层显像剂[O-(2-[¹⁸F]氟乙基)-L-酪氨酸的前体化合物：N-叔丁氧羰基-O-(2-甲磺酰/对硝基苯磺酰)-氧乙基-L-酪氨酸甲酯(9a,11a)和N-叔丁氧羰基-O-(2-甲磺酰/对甲苯磺酰/对硝基苯磺酰)-氧乙基-L-酪氨酸叔丁酯(9b,10b,11b)。 这些化合物以L-酪氨酸为原料,先与甲醇发生酯化反应或与乙酸叔丁酯进行酯交换,再用叔丁氧羰基保护氨基,最后以碳酸钾为碱、18-冠-6为相转移催化剂与乙二醇的磺酸酯在丙酮溶液中加热回流形成目标化合物,总收率为30%～67%。     

由脂肪族二酰胺二醇合成聚酯酰胺及表征

利用脂肪族二元酸酯与乙醇胺反应容易获得的对称二酰胺二醇,经缩聚合成聚酯酰胺预聚体,并针对端羧基和端羟基同时扩链来提高分子量,获得可生物降解的聚酯酰胺.首先将N,N′-二(2-羟乙基)草酰胺(HEOA)或N,N′-二(2-羟乙基)己二酰胺(HEHA)与己二酸和丁二醇缩聚,制备同时带有端羧基及端羟基的脂肪族聚酯酰胺预聚体,通过1,4-双(2-噁唑啉)苯及己二酰双己内酰胺混合扩链剂扩链,获得高分子量脂肪族聚酯酰胺,并通过红外、1H-NMR、DSC及TGA对其结构和热性能进行了表征.结果表明,预聚体在制备过程发生了一定的酯-酰胺交换反应;扩链后聚合物的熔点、熔融焓和热稳定性有所下降;但热稳定性仍接近或略高于聚己二酸丁二酯.     

酸性离子液体催化合成N-氰乙基-N-羟乙基苯胺

N-氰乙基-N-羟乙基苯胺是一种具有广泛用途的染料中间体,针对传统合成方法中的缺陷,以1-丁基-3-甲基咪唑硫酸氢盐([BMIM]HSO 4)为催化剂,丙烯腈和N-羟乙基苯胺为原料,建立了N-氰乙基-N-羟乙基苯胺的绿色合成新工艺。系统考察了离子液体种类、离子液体用量、底物比例等因素的影响规律,结果表明,[BMIM]HSO 4用量为0.8 mmol,n(N-羟乙基苯胺)∶[KG-*3/5]n(丙烯腈)=1∶[KG-*3/5]1.2,反应温度为90℃,反应时间为12 h时,N-氰乙基-N-羟乙基苯胺产率最高(89%),离子液体循环使用5次后,催化活性基本保持不变。     

α,β-聚[N-(丁二酸基)- L-天冬酰胺]的合成及其顺铂大分子药物的细胞毒性

L-天冬氨酸在H2O/三乙胺混合溶剂中直接均相开环聚(L-天冬酰亚胺)(PSI), 合成α,β-聚[N-(丁二酸基)-L-天冬酰胺](PSAA). 研究了H2O和三乙胺的混合体积比对反应物溶解性能的影响, 并用FTIR和1H NMR表征了PSAA的结构. 以PSAA和α,β-聚(L-天冬氨酸)(PAsp)为载体, 与顺式二氯二氨合铂(Ⅱ)(CDDP)络合, 合成了PSAA-CDDP和PAsp-CDDP大分子药物. 结果表明, 载体PSAA和PAsp对Bel7402细胞的毒性均低于同浓度的聚赖氨酸; PSAA-CDDP的水溶性良好, 载药量较高, 达到了14.6%, 其药物控制释放性能较好; PSAA-CDDP和PAsp-CDDP的细胞毒性随着其浓度的增大而增大, 且细胞毒性PAsp-CDDP相似文献   

由对苯二甲酰胺二醇合成聚酯酰胺及其扩链反应的研究

以N,N′-二(2-羟乙基)对苯二甲酰胺与己二酸及丁二醇缩聚,合成了同时带有端羧基与端羟基的聚酯酰胺预聚体,研究了不同扩链剂的扩链反应,获得了特性黏度达1.05 dL/g的聚酯酰胺.对预聚体及扩链后聚合物进行了红外与核磁表征,研究了聚合物的结构,并对聚合物进行了DSC与TG分析.     

N,N-二(2-羟乙基)-2-氨基乙磺酸钠的合成研究

采用二乙醇胺与2-氯乙基磺酸钠反应合成N,N-二(2-羟乙基)-2-氨基乙磺酸钠(BES钠盐),由核磁氢谱(1H NMR)和碳谱(13C NMR)、红外光谱(FT-IR)、X射线衍射(XRD)等仪器表征了合成产物的结构和特性.根据反应体系pH值的变化及核磁谱图,确定了BES钠盐的最佳合成工艺:反应物料比为1:1:1,反...     

六(乙氧基吡咯烷酮)三聚磷腈的合成与表征

以N-羟乙基吡咯烷酮与氢化钠作用生成相应的钠盐,再将此钠盐与六氯三聚磷腈(HCCP)发生亲核取代反应,合成了六(乙氧基吡咯烷酮)三聚磷腈,用IR、31P NMR、1H NMR、13C NMR、DEPT、FABMS等现代谱学技术对其结构进行了表征。生物活性试验表明,此化合物1mg/mL时对腐生线虫Panagrellus redivivus的72h致死率为52·7%。     

Preparation,characterization and thermal stability of poly[2-(Dimethylamino)ethyl acrylate]

Poly[2-(dimethylamino)ethyl acrylate] (PDAEA) and polymer complexes of 2-(dimethylamino)ethyl acrylate (DAEA) with nickel(II), copper(II), iron(III) and cobalt(II) chlorides were prepared and characterized by means of IR, electronic spectra and elemental analysis. The thermal stability of the homopolymer was compared with those of the polymer complexes, and the order of stability was given. The activation energies of the polymer complexes were calculated.     

水溶性荧光聚合物用于测定聚赖氨酸

合成了一种水溶性荧光聚合物聚[5-甲氧基-2-(3-磺酰化丙氧基)-1,4-苯撑乙烯](MPS-PPV),对该聚合物进行了元素分析、红外光谱及透射电子显微镜表征.实验结果表明,聚赖氨酸(PLL)对该聚合物荧光具有明显的猝灭作用,据此建立了一种快速灵敏测定聚赖氨酸的新方法,检出限为5.0×10^-10mol/L.探讨了聚赖氨酸猝灭MPS-PPV荧光的机理.     

5-[2-(8-羟基喹啉-2-基)乙烯基]-2-甲基-8-羟基喹啉的合成、抗氧化活性及促进鼠骨髓间质干细胞增殖的研究

设计合成了5-[2-(8-羟基喹啉-2-基)乙烯基]-2-甲基-8-羟基喹啉(5), 用IR, UV, ¹H NMR, MS和元素分析确认其结构. 利用DPPH•法和噻唑蓝比色法(MTT法)分别测定了目标产物的抗氧化活性及调控鼠骨髓间质干细胞(MSCs)增殖的作用. 结果表明, 目标产物有较强的抗氧化活性, 在低浓度时对鼠骨髓间质干细胞有促进作用.     

Polystyrene bis[N-(2-pyridyl) sulfonamide] palladium(II): Synthesis,characterization as a catalyst for coupling reactions

The [N-(2-pyridyl)] para-styrene sulfonamide (PSS) was prepared as a monomer, from the reaction of para-styrene sulfonyl chloride and 2-amino pyridine in the presence of potassium hydroxide solution 0.5 M as a base, and CH₃Cl. Polystyrene [N-(2-pyridyl) sulfonamide] (PPSS) was synthesized from the polymerization of [N-(2-pyridyl)] para-styrene sulfonamide (PSS). The Polystyrene bis [N-(2-pyridyl) sulfonamide] palladium (II) as a polymer- supporting palladium complex was also prepared from the reaction of PdCl₂ (CH₃CN)₂ with PPSS in the presence of KOH 0.5 M. Polystyrene bis [N-(2-pyridyl) sulfonamide] palladium (II) is produced as a novel heterogeneous catalyst for coupling reactions for C-C bond formation. This method includes higher yield and has an easier work-up procedure. The structures of the monomer, polymer and its Pd complex were confirmed by using FT-IR and ¹H-NMR spectroscopy. Elemental analysis of Pd by inductively coupled plasma (ICP) technique and hot filtration test showed loading of the metal into solution from the catalyst The heterogeneous catalyst was recycled without any loss in its properties.     

Saturated Nitrogen-containing Heterocycles. 20. Catalytic Reduction of N-Hydroxyethylpyridinium and Quinolinium Salts

Previously unknown N-(2-hydroxyethyl)perhydroquinolines and N-(2-hydroxyethyl)piperidines were synthesized by catalytic reduction of N-(2-hydroxyethyl)tetrahydroquinolinium and N-(2-hydroxyethyl)tetrahydropyridinium tetrafluoroborates. A scheme for the formation of the hydrogenation products is presented.     

Association behavior of one-end hydrophobically modified poly[<Emphasis Type="Italic">N</Emphasis><Superscript>5</Superscript>-(2-hydroxyethyl) <Emphasis Type="SmallCaps">l</Emphasis>-glutamine] in water/ethylene glycol mixed solvent

Amphiphilic polymers Cn-PHEG consisting of water-soluble poly[N ⁵-2-(hydroxyethyl) l-glutamine] (PHEG) and hydrophobic alkyl chain (carbon number n = 12, 14, 16, or 18) attached at the PHEG terminal was prepared, and association behavior and structure of associate for Cn-PHEG in selective solvent (water/ethylene glycol mixed solvent) have been investigated. α-Helix content of PHEG block for all the polymers increased with weight fraction of ethylene glycol in the mixed solvent (W _EG). By light scattering measurements, formation of a small micelle was suggested for C14-, C16-, and C18-PHEG when W _EG = 0. With the increase in W _EG, appearance of a larger associate was revealed for C16- and C18-PHEG. Evaluated molecular weight and radius of gyration suggested that the micelle is star-like sphere when W _EG = 0 and worm-like cylinder when W _EG = 0.7. C12-PHEG did not demonstrate any distinct micellization behavior because of the weak hydrophobicity of C12 chain.     

超声法合成聚[2-甲氧基-5-(2′-乙基己氧基)-对亚苯基亚乙烯基]的研究

采用超声合成方法,以对甲氧基苯酚为起始原料,经醚化、溴甲基化和聚合反应,得到无凝胶、完全可溶、高分子量的聚(2-甲氧基-5-(2′-乙基己氧基)-对亚苯基亚乙烯基)(MEH-PPV),其数均分子量高达9.5×105,分子量分布为2.4.并通过核磁共振氢谱(1H-NMR)和红外光谱进行了结构表征.与常规的机械搅拌反应相比,超声合成方法具有反应时间短、反应温度低、产率高、聚合物分子量较大等特点,特别是这种方法有效抑制了聚合过程中的凝胶化问题,合成的MEH-PPV具有更高的荧光量子效率.     

SYNTHESIS AND CHARACTERIZATION OF POLY{4-[2-(tert-BUTYLDIMETHYLSILOXY)ETHYL]STYRENE} AND ITS HYDROLYSIS DERIVATIVE

The living cationic polymerization of 4-[2-(tert-butyldimethylsiloxy)ethyl]styrene(TBDMES)was studied in methylcyclohexane(MeChx)/methylchloride(MeC1)(50/50 V/V)solvent mixture at-80℃.The initiator 1,1- diphenylethylene(DPE)capped 2-chloro-2,4,4-trimethylpentane(TMPCl)was formed in situ in conjunction with titanium tetrachloride(TiCl_4).The Lewis acidity of TiCl_4 was decreased by the addition of titanium(IV)isopropoxide(Ti(OiPr)_4)to accomplish living polymerization of TBDMES.Hydrolysis of poly(TBDMES)i...     

Structural Relationships Afforded by the Coordination of 2,2′-Bipyridine to the (Iminodiacetato)Copper(II) Chelate: Synthesis,Structure and Properties of (2,2′-Bipyridine) (N-(2-Hydroxyethyl)Iminodiacetato) Copper(II)Tetrahydrate

Abstract

The stoichiometric reaction of copper(II) hydroxycarbonate, N-(2-hydroxyethyl)iminodiacetic acid [H₂heida?HOCH₂CH₂N(CH₂CO₂H)₂)] and 2,2′-bipyridine (bipy) in water yields crystalline (2,2′-bipyridine)(N-(2-hydroxyethyl)iminodiacetato)copper(II) tetrahydrate, [Cu(heida)-(bipy)] · 4H₂O (compound I). This was studied by TG analysis (with FT-IR study of evolved gases), IR, electronic and ESR spectra, magnetic susceptibility data and single crystal X-ray diffraction methods. The compound crystallises in the triclinic system, space group P1, a = 7.011(2), b = 12.586(3), c = 13.052(3) Å, α = 62.14(1), β = 80.51(2), γ = 77.09(2)°, Z = 2, final R ₁ = 0.051 for 3900 independent reflections. The Cu(II) atom exhibits an asymmetric, elongated, octahedral coordination (type 4+1 + 1), and bipy acts as an N,N-bidentate ligand supplying two among the four closest donor atoms of the metal (Cu-N bond lengths of 1.994(2) and 2.053(2) Å); heida plays an N,O,O′,O″-tetradentate chelating role (bond lengths Cu?N = 2.075(2), Cu-O(carboxyl) = 1.958(2), Cu-O′(carboxyl) = 2.337(2) and Cu-O″(hydroxyl) = 2.459(2) Å). The effective bidentate chelation of bipy imposes fac-chelation to the iminodiace-tate moiety of heida in I, as previously reported in mixed-ligand complexes having a 1:1:2 Cu(II)/IDA/N(heterocyclic) or a 1/1/(1 + 1) Cu/IDA/(N-heterocyclic + N-aliphatic) donor ratio. The tetradentate role of heida in I reveals its noticeable conformational flexibility. The crystal features a hydrogen bond network forming supra-molecular chains extending along the a axis. These are linked by two symmetry-related hydrogen bonds of the type O(hydroxyl)-H…O′(carboxyl) between two adjacent complex units (symmetry code i=-x, -y+1, -z+1), related to each other by an inversion centre.