3,5-二硝基苯甲酸功能化的金属有机框架CAU-10-NH-DNBA荧光检测硫化氢

设计合成了一种基于3,5-二硝基苯甲酸功能化的金属有机框架CAU-10-NH-DNBA荧光探针,可直接用于H_(2)S的检测.首先,以三氯化铝和5-氨基间苯二甲酸为原料,在溶剂热条件下合成了金属有机框架CAU-10-NH_(2);然后,在水溶液中,以CAU-10-NH_(2)和3,5-二硝基苯甲酸(DNBA)为原料,在偶联剂1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)的共同作用下,合成了CAU-10-NH-DNBA.采用红外光谱、X射线衍射谱、固体核磁共振波谱、X射线光电子能谱和扫描电子显微镜对其进行了表征.结果表明,CAU-10-NH-DNBA的激发和发射波长分别为320和412 nm;H_(2)S可使CAU-10-NH-DNBA荧光增强;并考察了pH值、时间和温度对检测效果的影响.在最佳实验条件下,CAU-10-NH-DNBA对H_(2)S的检出限为2.43μmol/L,线性范围为3.9~62.5μmol/L,具有选择性高的优点.该探针可应用于人血清样品中H_(2)S含量的检测,样品回收率为94.5%~96.1%.

3,5-二羟基苯甲酸酯疏松纳滤膜的制备及染料/盐分离性能研究

为提高膜对印染废水的染料/盐分离效果,以3,5-二羟基苯甲酸为单体,通过低反应活性的羟基与均苯三甲酰氯(TMC)反应,在聚醚砜底膜表面通过界面聚合(IP)制备了新型聚酯疏松纳滤膜。对聚酯复合膜的化学组成、表面性质、表面形貌进行了表征,阐述了复合膜的结构性能关系,研究了不同的制备条件对复合膜的性能影响。在3,5-二羟基苯甲酸、氢氧化钠、均苯三甲酰氯质量分数分别为0.3%、0.2%、0.1%,界面聚合1 min的条件下,聚酯复合膜具有超高渗透性[水通量77.74 L/(m^(2)·h·bar)]、高染料截留率(刚果红,99.64%;直接红23,98.48%)和高盐渗透率(氯化钠,91.51%;硫酸钠,85.63%)。在2 bar压力下对染料/盐混合溶液进行5 h的过滤实验,所制复合膜表现出优异的防污性和运行稳定性。

3,5-二(2',5'-苯二羧酸)苯甲酸镍配合物的合成、结构及磁性

利用对称芳香多酸3,5-二(2',5'-苯二羧酸)苯甲酸(H_(5)L)和过渡金属镍,在水热法条件下,设计合成了一种新颖的金属有机配合物:{Ni(H_(3)L)(H_(2)O)}n(1),并通过单晶X射线衍射,红外光谱(IR),热重分析(TG)和粉末衍射对配合物1进行结构表征。结构分析表明1是基于多核[Ni(μ_(2)-H_(2)O)(μ_(2)-COO)(μ_(1)-COO)_(2)]_(n)SBUs的无限延伸的1D链状结构,并进一步通过π…π作用堆积成三维网络空间结构。磁性分析表明配合物1中的Ni(Ⅱ)离子之间存在反铁磁耦合作用。

β-(3,5-二叔丁基-4-羟基苯基)丙酰氯的合成研究

以β-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯为原料,通过水解反应和酰氯合成反应合成了抗氧剂中间体β-(3,5-二叔丁基-4-羟基苯基)丙酰氯。对酰氯合成条件进行了研究,得出优惠反应条件为:以氯仿作溶剂、β-(3,5-二叔丁基-4-羟基苯基)丙酸0.02mol、二氯亚砜0.054mol、反应温度50℃、反应时间5h,优惠条件下产品的收率为98.9%。

SYNTHESIS AND CHARACTERIZATION OF 2-(2-HYDROXY-3,5-DINITROPHENYLAZO)-7-(4-CHLORO-PHOSPHONPHENYLAZO)-1, 8-DIHYDROXY-NAPHTHALENE-3, 6-DISULF-ONIC ACID (CPAP) AS NEW REAGENT FOR DETERMINATION OF TOTAL PARE EARTHS

This paper reports the synthesis and general properties of the new reagent CPFP. Its dissociation constants have been determined. The characterization in determinating total RE with CPAP reagent has been investigated in detail. Analytic data for synthetic sample are satisfactory.

2,3,5,6-四氨基吡啶及其(2-羟基)对苯二甲酸复合盐的合成

为了制备高纯度与高收率的2,3,5,6-四氨基吡啶/2-羟基对苯二甲酸复合盐（TH盐），通过以2,6-二氨基-3,5二硝基吡啶（DADNP）为原料催化加氢还原制得2,3,5,6-四氨基吡啶盐酸盐（TAPH）。反应在55～60℃的氢气氛围下，以甲醇为溶剂，Pd/C为催化剂制得纯度99.4%的TAPH，收率82.1%。制成的盐酸盐再和2-羟基对苯二甲酸（HTA）钠盐在氮气氛围的保护下合成2,3,5,6-四氨基吡啶/2-羟基对苯二甲酸复合盐（TH 盐）单体，结构经过13C-NMR、MS和FT-IR表征分析，结果表明是目的产物，纯度达98%以上。

Synthesis and Crystal Structure of Glycin·3,5-Dihydroxybenzoic Acid

The title compound glycin.3,5-dihydroxybenzoic acid （GDB） has been synthesized and characterized by single-crystal X-ray analysis. It crystallizes in orthorhombic, space group Pca21 with a = 25.513（10）, b = 4.668（2）, c = 9.150（4） A°, Z= 4, V= 1089.8（8） A°^3, C9H13NO7, Mr= 247.20, Dc = 1.507 g/m^3,/z（MoKa） = 0.132 mm^-1, F（000） = 520, R1 = 0.0322 and wR2 = 0.0611 for 885 observed reflections （I 〉 2σ（I））. The title compound is a 1：1 molecular complex of glycin and 3,5-dihydroxybenzoic acid, which is linked by O-H…O and N-H…O hydrogen bonds to form a three-dimensional framework. Test of SHG （second harmonic generation） indicates that NLO generation of the crystal is higher than that of KDP.

Two Tetranuclear Zinc(Ⅱ) Coordination Polymers Based on 3,5-Bis(2-carboxylphenoxy)benzoic Acid with Highly Selective Sensing of Nitrobenzene

Two novel zinc（Ⅱ） coordination polymers, [Zn2（BCB）（CH3OH）（μ3-OH）]n（1） and {[Zn2（BCB）（μ3-OH）（H2O）2]·CH3OH}n （2）, have been constructed from 3,5-bis（2-carboxylphenoxy）benzoic acid（H3BCB） and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. Structural analysis reveals that complexes 1 and 2 are both 1D polymeric chains with unprecedented tetranuclear {Zn4（COO）4（μ3-OH）2} clusters, which were further expanded into a 2D structure. Fluorescence measurements show that 1 and 2 have highly selective and sensitive detection of nitrobenzene.

Syntheses, Crystal Structures and Luminescent and Magnetic Properties of Cerium(Ⅲ) and Zinc(Ⅱ) Coordination Compounds Constructed from 3,5-Dibromobenzoic Acid

Two coordination compounds, namely [Ce（3,5-Br2BC）3（3,5-HBrzBC）]n （1） and [Zn（3,5-Br2BC）2（phen）] （2, 3,5-HBr2BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a ID chain coordination network, which is further extended into a 3D supramolecular architecture via Br..＇Br and Br＇＂O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C-H..-O hydrogen bond, π-π stacking interactions and Br..π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.

Crystal Structure and Luminescence of a New Two-dimensional Sr(Ⅱ) Coordination Polymer Based on 3,5-Dinitro-salicylic Acid and 1,10-Phenanthroline

In this work, we report a new two-dimensional Sr（II） coordination polymer, namely, [Sr（L）（phen）（H20）] （1）, based on 3,5-dinitro-salicylic acid （H2L） and 1,10-phenanthroline （phen）. It crystallizes in monoclinic, space group P2/1 with a = 15.479（3）, b = 9.4020（19）, c = 13.884（3）/k, β= 103.76（3）°, V= 1962.5（7） A3, Z = 4, C19H12SrN4O8, Mr = 511.95, Dc = 1.733 g/cm^3, F（000） = 1024,μ（MoKa） = 2.805 mm^-1, R = 0.0411 and wR = 0.1069. In 1, each L anion bridges three Sr（II） atoms by using carboxylate and hydroxyl groups, yielding a two-dimensional layer structure. The phen ligands are alternately attached to both sides of the layer. The π-π stacking between L and phen in the same layer and hydrogen-bonding interactions between water molecule and carboxylate oxygen atom play an important role in stabilizing the layer structure of 1. The solid state luminescent property of 1 was also studied at room temperature.

3,5-二羟基苯甲酸转移加氢制备-3,5-二氧代环己烷羧酸

以3,5 二羟基苯甲酸为原料,采用Pd/C〔w(Pd)=5%〕催化剂,通过转移加氢法合成了3,5 二氧代环己烷羧酸。考察了适宜的催化剂制备及反应条件:浸渍制备的PdCl2/C经氢气还原,以甲酸钠为氢供体,水作溶剂,在90℃下反应2h,经HPLC分析得3,5 二氧代环己烷羧酸的收率为95%。得到的3,5 二氧代环己烷羧酸粗产物经柱层析分离得到纯品,并以1HNMR和元素分析法进行确证。催化剂经过XRD表征,确认了活性组分是原子态的Pd。并对催化剂失活原因做了初步分析。

Synthesis and Crystal Structure of One New Adduct of Isonicotinamide and 3,5-Dinitrosalicylic Acid

One new organic adduct,isonicotinamide·3,5-dinitrosalicylic acid with isonico-tin-amide（ina） and 3,5-dinitrosalicylic acid（3,5-dnsa） in 1：1 molar ratio,has been synthesized.Its struc-ture（C13H10N4O8,Mr = 350.25） was characterized by elemental analysis,IR and single-crystal X-ray diffraction analysis.The crystal belongs to the triclinic system,space group P1,with a = 8.812（4）,b = 9.487（5）,c = 9.604（6） ,α = 116.54（2）,β = 97.29（5）,γ = 98.35（4）°,V = 693.8（7） 3,Z = 2,Dc = 1.677 g/cm3,λ（MoKα） = 0.71073 ,μ = 0.142 mm-1,F（000） = 360,the final R = 0.0539 and wR = 0.1402 for 2417 unique reflections（Rint = 0.0288） with 1819 observed ones（Ⅰ 〉 2σ（Ⅰ））.Proton transfer reaction occurs between 3,5-dnsa and ina molecules,and the hydrogen bonds（N-H…O and C-H…O） with other interactions（π…π stacking and weak interactions of O…O and C…O） cooperatively construct a three-dimensional（3D） supramolecular structure.

3,5-二(3-羟基-2-吡啶氨基重氮基)-2,4,6-三溴苯甲酸的合成及其与铜的显色反应

本文合成了新显色剂3，5-二（3-羟基-2-吡啶氨基重氮基）-2，4，6-三溴苯甲酸（BHPADTBBA），并研究了该试剂与铜的显色反应，建立了分光光度法测定微量铜的新方法。结果表明，在pH10．0的Na2B4O7-NaOH缓冲溶液中，表面活性剂Triton X-100存在下，铜与BHPADTBBA生成络合比为1：2的红色络合物。该络合物在570nm处有最大吸收峰。检出限为7．8×10μg／mL。表观摩尔吸光系数为2．18×10^5L·mol^-1·cm^-1，铜量在0～18μg/25mL范围内符合比尔定律。所拟方法用于铝合金样品中铜的测定，结果同认定值相符。

Crystal Structure of Dimethylamine 3,5-Dinitrobenzoic Acid Organic Adduct

The title adduct （C9H11N3O6, Mr= 257.21） was synthesized and it crystallizes in orthorhombic, space group P212121 with a = 5.8835（19）, b =9.517（3）, c = 20.399（6） A, V= 1142.2（6） ,A^3 Z = 4, Dc= 1.496 g/cm^3, F（000） = 536,μ（MoKα） = 0.128 mm^-1, the final R = 0.0396 and wR = 0.0800 for 1047 observed reflections with I 〉 2σ（I）. The compound is a 1：1 adduct of dimethylamine and 3,5-dinitrobenzoic acid which are linked by hydrogen bonds to form a two-dimensional network. The dimethylamine is protonated at the nitrogen atom with the proton from the carboxyl of 3,5- dinitrobenzoic acid.

Synthesis,Mass Spectrometric Studies,and Biological Evaluation of 3,5-Dimethoxyhomophthalic Acid and Related Compounds

3,5-Dimethoxyhomophthalic acid was synthesized in four steps from 3,5-dimethoxycinnamic acid via a series of reactions including cyclization of 3-（3＇,5＇-dimethoxyphenyl）propionic acid to 5,7-dimethoxy-1-indanone and oxidative decomposition of methyl-2-hydroxy-2-[5,7-dimethyoxy-1-oxo-1H-inden-2（3H）-ylidene]acetate to 3,5-dimethoxyhomophthalic acid.The synthesized compounds were characterized by elemental analysis,IR,1H NMR,and MS.The biological evaluation experiments of 3,5-dimthoxyhomophthalic acid and the related synthesized compounds were also carried out.Naturally occurring biologically active isocoumarins were prepared in a single step by the condensation of the homophthalic acid with appropriate acid chlorides.

Crystal Structure of Nicotinic Acid·3,5-dinitrobenzoic Acid Organic Adduct

The title compound nicotinic acid3,5-dinitrobenzoic acid (NDNT) has been obtained by the reaction of nicotinic acid with 3,5-dinitrobenzoic acid in deionic water at room temperature. The crystal is of monoclinic, space group P21/n with a = 14.053(6), b = 5.046(2), c = 20.105(8) ? ?= 103.573(8)? C13H9N3O8, Mr = 335.23, Z = 4, V = 1385.8(10) 3, Dc = 1.607 g/cm3, (MoK? = 0.137 mm-1, F(000) = 688, R = 0.0435 and wR = 0.0993 for 1239 observed reflections (I > 2(I)). In the crystals, the asymmetric unit contains one nicotinic acid (C6H5NO2) and one 3,5- dinitrobenzoic acid (C7H4N2O6) molecules which are linked by some hydrogen bonds to form a twenty-membered hydrogen-bonded ring and an extended linear structure.

HIV病毒抑制剂中间体3,5-二羟基戊苯(olivetol)的新合成方法

以工业级的3,5-二甲氧基苯甲酸为起始原料,与L iH于室温下在四氢呋喃中反应5 h生成3,5-二甲氧基苯甲酸锂(Ⅰ),不需精制,直接与正丁基锂在冰浴中进行酰化反应制得3,5-二甲氧基苯戊酮(Ⅱ),收率85.06%;进而在210℃以下通过乌尔夫-黄鸣龙反应将Ⅱ还原为3,5-二甲氧基戊苯(Ⅲ),Ⅲ与熔融的吡啶盐酸盐在200℃回流2 h,脱甲基制得目标产物3,5-二羟基戊苯(Ⅳ),总收率为60.90%,质量分数为98.22%。利用IR1、HNMR、GC、HLPC-MS等分析手段对各步产物进行了表征。结果表明:该文所提出合成路线是可行的,具有工艺简单、收率高等特点,优于目前所报道的其他合成路线。目前正在进行放大实验。

Syntheses, Crystal Structures and Photoluminescence of Three Complexes Based on 3,5-(3-Carboxybenzyloxy)benzoic Acid

Three stable coordination polymers(CPs) assembled by 3,5-(carboxybenzyloxy)-benzoic acid(H3 L) and 1,10-phenanthroline(phen), namely, [Zn(HL)(phen)]n(1), [Cd(HL)(phen)]_n(2) and [Co(HL)(phen)]_n(3), have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, infrared(IR) spectroscopy and powder X-ray diffraction(PXRD). Investigation on crystal structure indicates that complexes 1 ～ 3 exhibit similar architecture. In these complexes, metal ions coordinate with H3 L and phen ligands, forming infinite 1 D chains. Then the adjacent chains combine together through intramolecular hydrogen-bonding interactions, generating 2 D supramolecular architectures. In addition, complexes 1～3 present excellent thermal stabilities and 1 and 2 exhibit strong luminescent emission bands at room temperature.

Synthesis and Crystal Structure of a Novel Organic Adduct Nonlinear Optical Material: 3,5-Dinitrobenzonic Acid·ethanolamine (3,5-DNBEA)

The title compound （C2H7NO·C7H4N2O6） has been obtained by the reaction of ethanolamine with 3,5-dinitrobenzoic acid in deionized water at room temperature. The crystal crystallizes in orthorhombic, space group P212121 with a = 6.048（2）, b = 9.146（3）, c = 21.955（7） A^°, C9H11N3O7, Mr = 273.21, Z = 4, V= 1214.3（7） , A^°3, Dc = 1.494 g/cm^3, F（000） = 568,μ（MoKα） = 0.131 mm^-1, R1 = 0.0338 and wR2 = 0.0497. The new organic adduct is composed of one ethanolamine and one 3,5-dinitrobenzoic acid, which are linked up by O-H…O and N-H…O types of hydrogen bonds to form a nine-membered ring and an eleven-membered ring, extending into a one-dimensional network structure.

3,5-二叔丁基-4-羟基苯基丙酸-1-膦-2,6,7-三氧双环-[2,2,2]辛基-4-甲酯的合成新工艺

以 3 - (3 ,5 -二叔丁基 - 4-羟基苯基 )丙酸甲酯 (简称 3 ,5 -甲酯 )、亚磷酸三乙酯、季戊四醇为原料 ,二丁基氧化锡为催化剂合成了标题化合物。考查了催化剂、反应温度、反应时间及物料配比等因素的影响 ,实验结果表明 :以 0 .1 mol季戊四醇为准 ,第一步和第二步反应温度分别为 1 1 0～ 1 2 0°C和 1 40°C,催化剂用量为 0 .6 g,反应时间为 5 h,n(季戊四醇 )∶n(亚磷酸三乙酯 )∶n(3 ,5 -甲酯 ) =1∶ 1∶ 1 .1 0 ,在此条件下 ,收率在 95 %以上。通过元素分析、红外光谱分析。