2-对溴苯基-5-芳基-1,3,4噁二唑类化合物的合成研究

设计并合成了3个2-对溴苯基-5-芳基-1,3,4-噁二唑类化合物,它们是进一步合成具有光电功能特性的噁二唑类化合物的重要前体。探讨了不同的合成条件和途径,发现以P(Ph)3/(Et)3N/CCl4作为脱水剂来合成非对称的1,3,4-噁二唑是较好的合成方法。     

2-(4-氯苯氧基)-5-芳基-1,3,4-噁二唑化合物的合成

首先以 4 氯苯酚为原料,在无水K2CO3、丙酮和KI的作用下,与氯乙酸乙酯反应制得 4 氯苯氧乙酸乙酯(Ⅰ),收率 85. 7%。再以无水乙醇为溶剂,于 105~110℃,与w(水合肼) =80%的反应 8h,制得 4 -氯苯氧乙酰肼(Ⅱ),收率 78 .2%。然后该化合物在以碳酸钠作缚酸剂,温度 40℃的条件下分别与苯甲酰氯、4 甲氧基苯甲酰氯、3, 5- 二甲基苯甲酰氯、4 甲基苯甲酰氯和 4 氯苯甲酰氯反应,得相应的N,N′- 二酰基肼(Ⅲa~e),收率分别为 90 .2%、89 .3%、85. 1%、91. 4%和 86 .1%。最后Ⅲa~e分别在POCl3 作用下,脱水环化成了 2- (4 -氯苯氧基)-5 -芳基 1, 3, 4 -口恶二唑化合物(Ⅳa~e),收率分别为 87 .2%、89 .6%、86. 1%、88. 4%和 84.3%。通过元素分析,IR,1HNMR和MS对化合物Ⅳa~e的结构进行了表征。     

1,3,4-(噁)二唑类化合物杀菌活性研究进展

1,3,4-二唑类化合物因其独特的生物活性在农药、医药等领域受到广泛关注.将1,3,4-二唑环引入不同的化合物结构中,通过结构修饰能生成一系列具有广谱生物活性的化合物.它在新型农药创制中发挥越来越重要的作用.按照不同的结构进行分类,从杀菌方面对1,3,4-二唑类化合物的生物活性研究进展进行了综述,重点介绍了该类化合物的一些生物活性研究方面的工作,并对它的发展趋势和应用前景作了展望.     

具有农药活性物1,3,4-噁二唑硫醚类化合物研究进展

1,3,4-噁二唑硫醚衍生物具有广谱生物活性,从抑菌、杀虫、除草及抗病毒等农药活性方面综述了1,3,4-噁二唑硫醚类化合物研究进展,期望为1,3,4-噁二唑硫醚衍生物在农业方面的应用提供依据。     

5-溴-1,3-二[2-(4′-叔丁基苯基)-1,3,4-(噁二唑基-5)]苯的合成

以5-氨基-1,3-苯二甲酸和对叔丁基苯甲酰肼为原料合成了一种新型电致磷光材料中间体5-溴-1,3-二[2-(4′-叔丁基苯基)-1,3,4-(噁二唑基-5)]苯,探讨了反应条件对合成反应的影响,反应的总收率为20.0%,方法可行。     

2-(4-氨基苯基)-5-(2-烷氧基苯基)-1,3,4-(噁)二唑的合成及表征

以对硝基苯甲酸和水杨酸甲酯为起始原料合成了两种新的1,3,4-噁二唑类化合物——2-(4-氨基苯基)-5-(2-乙氧基苯基)-1,3,4-噁二唑和2-(4-氨基苯基)-5-(2-戊氧基苯基)-1,3,4-噁二唑。合成过程中,1,3,4-噁二唑化合物上的硝基采用钯碳催化氢化的方法还原成氨基,使后处理变得容易,产率显著提高,分别达98.4%和96%。通过IR和1HNMR确证了相关化合物的结构。     

(4-取代苯甲酰基)双-1,3,4-噁二唑化合物的合成

双-1,3,4-噁二唑类化合物因其特殊的分子结构而易与金属离子形成络合物,所以在金属缓蚀上是一类具有前景的化合物。以癸二酸和甲醇为起始原料,经过酯化,肼解,酰化,缩合等反应,得到一系列（4-取代苯甲酰基）双-1,3,4-噁二唑,通过红外光谱和核磁共振氢谱对其结构进行了表征。     

超声辅助2-取代硫醚-5-[5-(4-硝基苯基)-1H-吡唑-3-基]-1,3,4-噁二唑类化合物的合成

以5-(4-硝基苯基)-1 H-吡唑-3-甲酸乙酯(1)为起始原料,经肼解和关环合成了中间体5-[5-(4-硝基苯基)-1 H-吡唑-3-基]-2-巯基-1,3,4-噁二唑(3)。在超声作用下,以乙腈为溶剂,固体K2CO3为缚酸剂,使化合物3与卤代烃反应合成4个含取代吡唑基的1,3,4-噁二唑硫醚类化合物4a～4d,该法具有反应时间短、产率较高和操作简便等特点。产物结构经元素分析、IR、1 H NMR表征。     

3-N-丙酰基-2-芳基-5-(2-溴-5-氟苯基)-1,3,4-(噁)唑啉类衍生物的合成与结构表征

2-溴5-氟苯甲酰肼(1)与芳香醛缩合得到酰腙(2a～2i),再与丙酸酐环合成了3-N-丙酰基-2-芳基-5-(2-溴-5-氟苯基)-1,3,4-噁唑啉类衍生物(3a～3i),收率70%～83%。化合物的结构经元素分析、IR、1HNMR和MS确证。     

一种新的铕配合物Eu(BTI)3DPPZ的合成及光致发光

合成并表征了可溶性双(硫代磷酰基)亚胺铕配合物Eu(BTI)3DPPZ,在挥发性溶剂中具有好的溶解性,TG表明它具有较高的热稳定性。在345nm的激发波长下,Eu(BTI)3DPPZ的最强发射波长在612nm,这是铕离子的特征发射谱线,归属于5D0→7F2。从发光强度来看,Eu(BTI)3DPPZ的光致发光产生了较强的红光。     

Synthesis and photoluminescence properties of Eu2+/Eu3+ or Ce3+/Eu3+ co-doped Sr5(BO3)3F compounds

The synthesis and photo-luminescence properties of Eu²⁺/Eu³⁺ or Ce³⁺/Eu³⁺ co-doped Sr₅(BO₃)₃F compounds are reported. Using the Sr₅(BO₃)₃F as the host, through the solid state reaction under the reductive atmosphere, Eu²⁺/Eu³⁺ and Ce³⁺/Eu³⁺co-doped samples were prepared. These compounds exhibit good photo-luminescence properties. Under the excitation of 376 nm, an unusual red orange emission coming from the Eu²⁺ ions can be obtained in Eu ions doped Sr₅(BO₃)₃F, which exhibits a broadband emission in the range of 450–800 nm with the peak at around 600 nm. At the same time, the characteristic f-f excitation and emission of Eu³⁺ can improve and adjust the Eu²⁺ emission in Eu³⁺/Eu²⁺ codoped Sr₅(BO₃)₃F. In addition, the adjustable luminescence properties from blue to white of Sr₅(BO₃)₃F:Ce³⁺, Eu³⁺ are investigated. The energy transfer behavior from Ce³⁺ to Eu³⁺ was confirmed. In the spectra of the co-doped samples, we can hardly observe the characteristic peak of Eu²⁺, because Ce⁴⁺ can oxidize Eu²⁺ to Eu³⁺, and Ce⁴⁺ itself is reduced to Ce³⁺. The CIE coordinates from (0.2758, 0.2420) to (0.3857, 0.3015) show Sr₅(BO₃)₃F:3%Ce³⁺, x%Eu³⁺ (x = 1,3,5,7,9) are in the white light emission region. All results demonstrate that the Sr₅(BO₃)₃F:Eu³⁺/Eu²⁺ and Sr₅(BO₃)₃F:Ce³⁺/Eu³⁺ phosphors have good application prospects for LED plant growth and white LED, respectively. The bond energy method was used to explain the reason why the Eu²⁺/Eu³⁺ ion instead of only Eu²⁺ and Ce³⁺/Eu³⁺ instead of Ce³⁺/Eu³⁺/Eu²⁺ can exist in the host Sr₅(BO₃)₃F. The theoretical analysis agree well with the experimental result.     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Y(PO4)3 red phosphors

A series of red-emitting phosphors Eu³⁺-doped Sr₃Y(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Y(PO₄)₃:Eu³⁺ phosphors exhibit peaks associated with the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The integral intensity of the emission spectra of Sr₃Y_0.94(PO₄)₃:0.06Eu³⁺ phosphors excited at 392 nm is about 3.4 times higher than that of Y₂O₃:Eu³⁺ commercial red phosphor. The Commission Internationale de l’Eclairage chromaticity coordinates, the quantum efficiencies and decay times of the phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Y(PO₄)₃ phosphors are promising red-emitting phosphors pumped by near-UV light.     

Synthesis and photoluminescence properties of CaGd2(MoO4)4:Eu3+ red phosphors

The novel red-emitting Eu³⁺ ions activated CaGd₂(MoO₄)₄ phosphors were prepared by a citrate sol–gel method. The X-ray diffraction patterns confirmed their tetragonal structure when the samples were annealed above 600 °C. The photoluminescence excitation spectra of CaGd₂(MoO₄)₄:Eu³⁺ phosphors exhibited the charge transfer band (CTB) and intense f–f transitions of Eu³⁺ ion. The optimized annealing temperature and Eu³⁺ ion concentration were analyzed for CaGd₂(MoO₄)₄:Eu³⁺ phosphors based on the dominant red (⁵D₀→⁷F₂) emission intensity under NUV (394 nm) excitation. All decay curves were well fitted by the single exponential function. These luminescent powders are expected to find potential applications such as WLEDs and optical display systems.     

YVO4:Eu3+,Bi3+荧光粉的制备及荧光性能研究

用溶胶凝胶法在较低温度下制备了YVO4:Eu3+,Bi3+荧光粉,采用X射线衍射仪(XRD),扫描电子显微镜(SEM)及荧光分光光度计测试,研究了合成产物的结构、表面形貌,分析了在Eu3+含量一定的情况下掺杂Bi3+的浓度的变化对发光性能的影响.结果表明,溶胶凝胶法合成的YVO4:Eu3+,Bi3荧光粉为单相结构、粒径在1 μm左右、无团聚现象;Bi3+对Eu3+离子有敏化作用,在一定浓度下使荧光粉的发射强度增加.     

Synthesis and photoluminescence of the Eu3+ composite with dibenzoylmethane and oligoacrylic acid

An Eu³⁺–dibenzoylmethide (DBM) –oligoacrylic acid (OAA) composite was prepared in water, ethanol, and a glycerin mixed solvent. Influence of pH value on the synthesis was also given. A composite with pH of 10.0 was most suitable for the synthesis. It was confirmed by UV–VIS, Fourier transform infrared (FTIR), excitation spectra, and conductivity measurement that DBM, the second ligand, which had low molecular weight, coordinated with Eu³⁺ in the ionomer chain, instead of dispersing in the OAA matrix. When the molar ratio of DBM–Eu³⁺ was 2:1, which was found to be the best ratio to obtain the maximum intensity of fluorescence (due to the ⁵D₀→⁷F₂ transition), the fluorescence intensity of the Eu³⁺– DBM–OAA (emitted at 616 nm) increased logarithmically with the increase of the molar ratio of Eu³⁺–OAA in the range of 0 to 6 : 1. Energy transfer in the composite was also discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2588–2593, 1999     

Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I) complex [Cu(ABPQ)(DPEphos)]BF₄ [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h;3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF₄ are attributed to the ligand-centered π → π* transition and the metal-to-ligand charge transfer dπ(Cu) → π*(N–N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF₄ in CHCl₃ is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF₄.     

Synthesis,crystal structure and self-assembly property of a mixed (phthalocyaninato) (porphyrinato) europium triple-decker complex

A mixed phthalocyaninato and porphyrinato triple-decker complex [Eu₂(Pc)₂(TClPP)] was synthesized and characterized by elemental analysis, FT-IR, UV, and X-ray structure determination. Its self-assembling properties in mixed chloroform/methanol solution were investigated by TEM, SEM and XRD techniques. Investigation revealing the availability of the single crystal, together with the molecular structure, renders it possible to investigate the formation mechanism as well as the molecular packing conformation of self-assembled nanostructures fabricated from this complex in a more confirmed manner.     

Eu(3+)-β-二酮、三正辛胺三元配合物的合成与光谱特性

合成了铕(Ⅲ)的二苯甲酰甲烷、三正辛胺的三元配合物Eu(3+·(DBM)3·[N(C8H(17))3]2，通过元素分析确定了配合物的组成，并通过红外光谱对配合物进行了表征。结合红外光谱、荧光光谱讨论了配合物的成键特性、配体传能机制以及协同配体N(C8H(17))3引入对激发光谱的影响。荧光光谱表明配合物可吸收247～400nm的宽带紫外光，发射Eu(3+)的5D0→7F2对应的612nm红色荧光。适于用作农膜转光剂。     

Synthesis,structural characterization,and photoluminescence properties of Eu3+‐doped Mg3‐xEux(BO3)2 phosphor

Eu³⁺‐doped Mg_3‐xEu_x(BO₃)₂ (x = 0.000, 0.005, 0.010, 0.020, 0.050, and 0.100) phosphors were synthesized for the first time by solution combustion synthesis method, which is a fast synthesis method for obtaining nano‐sized borate powders. The optimization of the synthesis conditions of phosphor materials was performed by TG/DTA method. These phosphors were characterized by XRD, FTIR, SEM‐EDX, and photoluminescence, PL analysis. The XRD analysis exhibited that all of the prepared ceramic compounds have been crystallized in orthorhombic structure with space group Pnnm. Also, the influence of europium dopant ions on unit cell parameters of host material was analyzed using Jana2006 program and the crystalline size was determined by Debye‐Scherrer's formula. The luminescence properties of all Eu³⁺‐doped samples were investigated by excitation and emission spectra. The excitation spectra of Mg_3‐xEu_x(BO₃)₂ phosphors show characteristic peak at 420 nm in addition to other characteristic peaks of Eu³⁺ under emission at 613 nm. The emission spectra of Eu³⁺‐doped samples indicated most intensive red emission band dominated at 630 nm belonging to ⁵D₀→⁷F₂ magnetic dipole transition. Furthermore, the optimum or quenching concentration of Eu³⁺ ion has been determined as x = 0.010 showed the maximum emission intensity when it was excited at 394 nm.