Study on thermal decomposition kinetics of azobenzene-4,4′-dicarboxylic acid by using compensation parameter method and nonlinear fitting evaluation

Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application in the future,the thermal stability of this substance during storage,transportation,and use will become quite important.Thus,in this work,the thermal decomposition behavior,thermal decomposition kinetics,and thermal hazard of ADCA were investigated.Experiments were conducted by using a SENSYS evo DSC device.A combination of differential iso-conversion method,compensation parameter method,and nonlinear fitting evaluation were also used to analyze thermal kinetics and mechanism of ADCA decomposition.The results show that when conversion rate α increases,the activation energies of ADCA's first and main decomposition peaks fall.The amount of heat released during decomposition varies between 182.46 and 231.16 J·g^(-1).The proposed kinetic equation is based on the Avrami-Erofeev model,which is consistent with the decomposition progress.Applying the Frank-Kamenetskii model,a calculated self-accelerating decomposition temperature of 287.0℃is obtained.

基于4-羟基间苯二甲酸和含氮杂环配体的Zn(Ⅱ)配合物的合成、晶体结构与荧光性质研究

在水热法条件下,4-羟基间苯二甲酸(H 2HPHA)和锌离子分别与1,2二(吡啶-4-基)乙烯(dpee)及4,4′-联吡啶(4,4′-bpy)反应得到了2个三维的配位聚合物[Zn(HPHA)(dpee)·(DMA)2]n(配合物1)和[Zn(HPHA)2(4,4′-bpy)2·DMA]n(配合物2)。用X射线单晶衍射测定了配合物的晶体结构,结果显示:配合物1属于单斜晶系,C2空间群,每个不对称单元由一个锌离子,一个4-羟基间苯二甲酸配体及一个1,2-二(吡啶-4-基)乙烯组成;配合物2属于单斜晶系,P12/c1空间群,每个不对称单元由两个锌离子,两个4-羟基间苯二甲酸配体及两个4,4′-联吡啶配体组成。荧光光谱分析结果表明:配合物1的最强激发峰和发射峰在分别在251和397 nm,配合物2的最强激发峰和发射峰分别在415和513 nm。热重分析表明两个配合物在室温下稳定。

3,3’,4,4’-联苯四甲酸合成用Pd/C催化剂制备工艺研究

采用浸渍沉淀法制备3,3’,4,4’-联苯四甲酸合成用Pd/C催化剂,考察不同沉淀剂、还原剂对Pd/C催化剂性能的影响,发现使用不同沉淀剂和还原剂时,催化剂活性及3,3’,4,4’-联苯四甲酸收率存在明显差异,硼氢化钠还原的Pd/C催化剂活性及3,3’,4,4’-联苯四甲酸收率最高。进一步考察助金属协同催化作用对Pd/C性能的影响,结果表明,Pd/C中添加质量分数1.0%Mn后催化剂活性及3,3’,4,4’-联苯四甲酸收率均有所提高。

Two 3D Metal-organic Frameworks with 4-Fold [2＋2]-type Interpenetrated hms Nets Based on a Flexible Tricarboxylic Acid

Two 3D 4-fold interpenetrated metal-organic frameworks, [Mn（L）（bpy）]n （1） and [Cu（HL）（bpy）]n （2）（H3L = 4,4＇,4＇＇-（benzene-1,3,5-triyl-tri（methyleneoxy）） tribenzoic acid, bpy = 4,4′-bipyridine）, were synthesized under hydrothermal conditions, and characterized by element analyses, IR spectra, thermogravimetric analyses, X-ray powder diffraction and magnetic property studies. The single-crystal X-ray analyses revealed that 1 and 2 are homogeneous. 1 crystallizes in monoclinic, space group Cc with a = 26.794（2）, b = 11.6346（10）, c = 21.4614（18） ？, β = 91.570（2）°, V = 6687.9（10） A^3, Z = 8, Mr = 736.59, D = 1.463 g·cm^（-3）, μ = 0.458 mm^-1c, R（int） = 0.0524, F（000） = 3040, the final R = 0.0844 and wR = 0.2266 for 8092 observed reflections（I 〉 2σ（I））. 2 crystallizes in monoclinic, space group Cc with a = 27.609（12）, b = 11.126（10）, c = 21.490（9） ？, β = 92.131（2）°, V = 6597（5） A^3, Z = 8, Mr = 746.21, Dc = 1503 g·cm^（-3）, μ = 0.726 mm^-1, R（int） = 0.0542, F（000） = 3080, the final R =0.0681 and wR = 0.1831 for 6777 observed reflections（I 〉 2σ（I））. Two compounds are 3D [2＋2]-type 4-fold interpenetrated frameworks with（6^3）（6^9.8） hms topology. The magnetic study of compound 2 shows the presence of weak antiferromagnetic interaction between the Cu^Ⅱ ions in 2.

基于4,4’-偶氮苯二甲酸的金属-有机框架合成及其荧光性质

分别以吡嗪和4,4’-联吡啶为共配体,Cd^(2+)、Zn^(2+)与4,4’-偶氮苯二甲酸(H 2(4,4’-azo))配位反应得到了两个金属-有机框架(MOFs)。X射线单晶衍射研究结果表明,其结构中均不含共配体,与之前报道的[Cd(4,4’-azo)(H 2 O)]n(1)和[Zn(4,4’-azo)(H 2 O)2]n(2)的晶体结构一致。将共配体变为几何尺寸更长的1,3-二(四吡啶基)丙烷(bpp),金属离子变为Co^(2+),合成了一个共晶[H 2(4,4’-azo)(bpp)]n(3),其为单斜晶系,C2/c空间群,晶胞参数:a=3.2168(19)nm,b=0.4755(3)nm,c=1.8732(14)nm。用热重分析仪和荧光分光光度计分别研究了三个化合物的热稳定性和两个MOFs的发光性质。1和2都具有优异的热稳定性,尤其是2的初始失重温度高达247℃。由于1是由4,4’-azo双齿配位两个Cd^(2+)形成双核3D网络结构,而2是4,4’-azo单齿配位Zn^(2+)形成的1D“zig-zag”链,两者的紫外光谱和荧光光谱不同。2除具有配体固有的荧光发射(359 nm)外,由于Zn^(2+)与4,4’-azo配位后产生的配体到金属的电荷跃迁(LMCT),还在420 nm处新增一个增强的荧光发射峰。

基于4,4’-磺酰基二苯甲酸配体构筑的稀土有机框架及荧光传感性能研究

在溶剂热条件下,以4,4’-磺酰基二苯甲酸(H_(2)SDBA)为配体与硝酸铕构建出具有荧光性质的稀土有机框架[Eu_(2)(SDBA)_(3)(H_(2)O)_(4)]·NMP(NMP=N-甲基吡咯烷酮),并对其进行粉末X射线衍射、荧光光谱、紫外吸收光谱等手段表征.X射线单晶衍射分析结果显示该材料具有三维结构.Eu-MOFs具有良好的荧光性能,能够在水中同时实现对维生素B4和阿奇霉素的高灵敏及高选择的荧光淬灭检测.

pH Dependent Supramolecules Based on Co-crystallization of Pyrazine-2,3,5,6-tetracarboxylic Acid with 4,4＇-Bipyridine through Intermolecular Hydrogen Bonds

Co-crystallization of pztcH_4 with 4,4＇-bipyridine（4,4＇-bipy） in pH = 3-4 and 1-2 gave two new binary molecular adducts： [（4,4＇-bipy H2）（pztc H2）]（1） and [（4,4＇-bipy H2）（pztcH3）（Cl）]·4H2O（2）, respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 5.7752（12）, b = 7.9126（16）, c = 9.4492（19） ？, α = 97.49（3）, β = 107.71（3）, γ = 94.52（3）o, V = 404.62（14） A^3, Z = 1, μ = 0.137 mm^1, Dc = 1.692 Mg/m^3, C18H12N4O8, Mr = 412.32, F（000） = 212, S = 1.025, R = 0.0360 and wR = 0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a = 17.093（3）, b = 7.7665（16）, c = 18.414（4） A, β = 113.36（3）o, V = 2244.1（8） A^3, Z = 4, μ = 0.244 mm^-1, Dc = 1.542 Mg/m^3, C18H21ClN4O12, Mr = 520.84, F（000） = 1080, S = 1.021, R = 0.0343 and wR = 0.0978. In compound 1, pztc H22- anions self-formed 2-D sheets by strong Oacid-H···Oacidhydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4？-bipy via N-H···Oacid interactions. In compound 2, besides the 1-D chain constructed by pztc H3-itself through strong H-bond Oacid-H···Oacid, the other chain is constructed with 4,4？-bipy H22＋, Cl-anion and water molecules by moderate H-bonds and Ow-H···Cl and N-H···Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding Oacid-H···Ow to afford an interlaced 3-D network.

Synthesis,Crystal Structure and Theoretical Calculations of a Nickel(Ⅱ) Coordination Polymer Assembled by 4,4'-Oxydibenzoic Acid and 1,3-Bis(imidazol-1-ylmethyl)-benzene Ligands

A new metal-organic coordination polymer [Ni（oba）（mbix）（H2O）]n·n H2O（H2oba = 4,4‘-oxydibenzoic acid,mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR,TG,UV and single-crystal X-ray diffraction.Green crystals crystallize in the triclinic system,space group P1 with a = 10.1915（18）,b = 11.415（2）,c = 12.314（2）A,α = 74.263（3）,β = 84.545（2）,γ = 74.369（3）o,V = 1327.6（4） A,C28H26N4 Ni O7,Mr = 589.24,Dc = 1.474 g/cm3,F（000） = 612,Z = 2,μ（Mo Kα） = 0.786 mm-1,the final R = 0.0332 and w R = 0.0869 for 4622 observed reflections（I 〉 2σ（I））.The structure of 1 exhibits a one-dimensional chain-like structure.In addition,natural bond orbital（NBO） analysis was performed by the PBE0/LANL2 DZ method in Gaussian 03 Program.The calculation results show obvious covalent interaction between the coordinated atoms and Ni（Ⅱ） ion.

Solvothermal Synthesis and Structure of the [Co(5-NH_2-bdc)(4,4'-dpdo)(H_2O)]_n Complex (4,4'-dpdo = 4,4'-Bipyridrl-N,N'-dioxide,5-NH_2-bdc = 5-Aminoisophthalic Acid)

The title compound [Co（5-NH2-bdc）（4,4＇-dpdo）（H2O）]n 1 （5-NH2-bdc = 5-aminoiso- phthalic acid,4,4＇-dpdo = 4,4＇-bipyridrl-N,N＇-dioxide） crystallizes in triclinic,space group P1 with a = 4.999（1）,b = 10.072（2）,c = 13.028（3） A,α = 107.72（3）,β = 92.58（3）,γ = 98.11（3）°,V = 615.9（3） A^3,F（000） = 356,Rint = 0.0186,Z = 2,R = 0.0333,wR = 0.0721,S = 1.032 and （Δ/σ）max = 0.001. In the molecule of 1,the Co（II） cation is coordinated by three O-atoms of two 5-NH2-bdc ligands,one N-atom of another 5-NH2-bdc ligand,one O-atom of 4,4＇-dpdo and one terminal O-atom of water molecule. The molecules construct a 2-D network through bridging 5-NH2-bdc and 4,4＇-dpdo ligands,and further form a 3-D network through N–H and O–H hydrogen bonds. The network topology of 1 can be simplified as a rare 2D （3,6）-connected （426381） net.

4,4′-联苯二甲酸合成工艺研究

以医药中间体合成过程中产生的副产物4,4′-二甲基联苯为原料,经氯代反应生成4,4′-双(三氯甲基)联苯,然后水解制得4,4′-联苯二甲酸;对氯代反应的历程进行了探讨,并通过正交实验考察了反应参数对4,4′-联苯二甲酸收率的影响,得到了优化工艺条件,优化工艺条件下的验证实验表明:反应总收率达到93.40%,纯度达99.20%。采用IR、~1HNMR对产物的结构进行表征,通过HPLC对生成的4,4′-联苯二甲酸的纯度进行测定。该合成工艺具有环境友好、工艺操作简单、转化率及收率高、经济性好等优点,适合工业化大规模生产。

一个由4,4′-(丁烷-1,4-二氧基)-二苯甲酸和双咪唑配体构筑的三重穿插金属有机骨架化合物(英文)

采用水热法合成了1个二维缠结金属有机框架化合物[Cu(bbi)0.5(boba)]n(1)(bbi=1,1′-(1,4-丁烷基)-二(咪唑);H2boba=4,4′-(丁烷-1,4-二氧基)-二苯甲酸),并通过元素分析、红外光谱和单晶X-射线衍射对其进行了结构表征。结构分析显示:化合物1是具有聚轮烷和聚锁烃结构特征的三重平行穿插网络。此外还研究了它的荧光和热稳定性。

三苯甲醇-4,4′,4″-三羧酸及其氯化物的合成

以4-溴甲苯为原料,合成了几种三芳基甲烷衍生物:三甲苯甲醇(TTMO)、三苯甲醇-4,4′,4″-三羧酸(TOTA)、三苯基氯甲烷-4,4′,4″-三羧酸(TClTA);利用红外光谱仪、核磁共振谱仪及元素分析仪表征了合成产物的结构和组成.结果表明,将4-溴甲苯与镁条在四氢呋喃中反应,可得到对甲苯基溴化镁;对甲苯基溴化镁随后与碳酸二乙酯反应,可得到TTMO;TTMO经硝酸氧化得到TOTA;TOTA与乙酰氯反应得到TClTA.

4,4’-双(三氯甲基)联苯水解合成4,4’-联苯二甲酸工艺研究

以副产物4,4’-双(三氯甲基)联苯为原料,经碱性水解一步反应合成出4,4’-联苯二甲酸。考察反应物料摩尔比、反应温度、反应时间对4,4’-联苯二甲酸产品收率的影响,得到优化工艺条件:氯苯为溶剂,4,4’-双(三氯甲基)联苯与10%氢氧化钠溶液的摩尔比为1∶9,反应温度为105℃,反应时间为14 h。在上述条件下,4,4’-联苯二甲酸的收率为95.25%,纯度可达99.20%,通过红外光谱、核磁共振氢谱及高效液相色谱等对产物进行了表征。

4-氯苯氧乙酸及4,4′-bipy=4,4′-联吡啶构筑的层状锌配合物的合成、晶体结构(英文)

水热条件下,合成了一个新的锌(Ⅱ)配位聚合物[Zn(PCPA)2(4,4′-bipy)(H2O)]n(PCPA=4-氯苯氧乙酸,4,4′-bipy=4,4′-联吡啶),并通过元素分析、红外光谱、紫外光谱、热重分析、X-射线粉末衍射和X-射线单晶衍射对其进行了表征。锌(Ⅱ)分别与来自2个4,4′-bipy的2个氮原子、3个4-氯苯氧乙酸的3个氧原子和1个水分子中的1个氧原子配位,形成变形的八面体的配位构型。由于4-氯苯氧乙酸和4,4′-bipy的桥联作用,配合物在空间形成了二维层状结构,在此二维层状结构中存在的O-H…O氢键起到了稳定结构的作用。

Synthesis, Structure and Photoluminescent Property of a New 3D Cd(Ⅱ) Coordination Polymer with Terphenyl-2,2',4,4'-tetracarboxylic Acid and 1,10-Phenanthroline

A new 3D Cd（II） coordination polymer, [Cd2L（phen）（HzO）]n （1, HaL = terphenyl- 2,2＇,4,4＇-tetracarboxylic acid, phen = 1,10-phenanthroline）, has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, TGA and IR spectroscopy. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 8.196（2）, b = 18.348（5）, c = 19.036（5） A, β = 97.741（5）°, V= 2836.6（14） A3, Z = 4, Dc = 1.933 Mg.m-3, p = 1.565 mm1, F（000） = 1624, the final R = 0.0356 and wR = 0.0612 for 4990 observed reflections with 1 〉 2a（I）. Complex 1 has a 1D chain containing Cd4 structural units, which are linked by 2- and 2＇-carboxyl groups of L4- to result in a 3D framework. Additionally, the photoluminescent property of 1 was also studied in the solid state at room temperature.

〔~3H-4,4′-〕二苯羟乙酸-3-奎宁环酯的合成

本文报道了由4,4′-二溴二苯羟乙酸-3-奎宁环酯在10％钯-炭催化卤氚交换法制备了[~3H-4,4′-]二苯羟乙酸-3-奎宁环酯,它的放射性比度851GBq/mmol,放射性化学纯度大于98％。

Syntheses and Crystal Structures of Two Co(II) Coordination Polymers with 4,4'-(Hexafluoroisopropylidene)bis(benzoic acid)

Two new one-dimensional zigzag chain coordination polymers, [Co（hfipbb）（2,2＇- bpy）（H2O）2]n 1 and [Co（hfipbb）（1,10-phen）（H2O）], 2, have been synthesized under hydrother- mal reactions from COCl2.6H20, 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid） and 2,2＇ -bipyridine or 1,10-phenanthroline ligands, respectively. Single-crystal X-ray analyses revealed that the zigzag chains of 1 and 2 are linked into three-dimensional supramolecular networks by both O-H…O hydrogen-bonds and π…π stacking interactions. Crystal data for 1： CzTHajCoF6N2Os Mr = 641.38, orthorhombic, space group Pnna, a = 9.3820（19）, b = 27.366（6）, c = 10.106（2）A, V = 2594.8（9）A3, Z = 4, Dc = 1.642 g/cm3, F（000） = 1300,/t = 0.752 mm-l, R = 0.0311 and wR = 0.0924. Crystal data for 2： C29H18CoF6N2O5, Mr = 647.38, monoclinic, space group P21/n, a = 7.7626（16）, b = 29.446（6）, c = 11.281（2）A,β= 93.98（3）°, V= 2572.3（9）A3, Z = 4, Dc = 1.672 g/cm3, F（000） = 1308,μ= 0.757 mm-1, R = 0.0403 and wR = 0.0820.

A One-dimensional Pseudo-helical Coordination Polymer with 4,4′-(Hexafluoroisopropylidene)bis(benzoic acid)

The title complex [Zn2（hfipbb）2（2,2′-bpy）2], 1 has been hydrothermally synthesized from Zn（NO3）2·6H2O, 4,4′-（hexafluoroisopropylidene）bis（benzoic acid） and 2,2′-bipyridine. Singlecrystal X-ray analysis reveals that 1 presents a one-dimensional coordination polymer with pseudo-helical chain structure. Two Zn（Ⅱ） atoms in an unsymmetrical unit of 1 adopt distorted octahedral and square-pyramidal coordination geometries, respectively. The packing of parallel chains gives a three-dimensional supramolecular network supported by π-π stacking interactions. Crystal data： C54H32F12N4O8Zn2, Mr = 1223.58, monoclinic, space group P2 1/c, a = 27.557（6）, b = 16.751（3）, c = 11.350（2） A, β= 99.21（3）°, V= 5171.5（18） A^3, Z= 4, Dc = 1.572 g/cm^3, F（000） = 2464, μ= 1.030 mm^-1, the final R = 0.0552 and wR = 0.1070 for 6631 observed reflections （I〉 2σ（I））.

Synthesis and Characterization of a New 3D Pillared Bilayer Cd(Ⅱ) Coordination Polymer Based on 6,6?-Dinitro-2,2?,4,4?-biphenyltetracarboxylic Acid

A new 3D Cd（II） coordination polymer, [Cd2L（dpe）]n （1, HaL = 6,6＂-dinitro-2,2＂,4, 4＂-biphenyltetracarboxylic acid, dpe = 1,2-di（4-pyridyl）ethylene）, has been synthesized using the hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, IR, thermogravimetric analysis, and photoluminescent analysis. Complex 1 crystallizes in the monoclinic system, space group C2/c with a = 8.0006（15）, b = 23.900（5）, c = 14.836（3） A, fl = 95.723（3）°, V = 2822.7（10） A3, Z = 8, Dc = 1.937 Mg.m3, p = 1.581 mm-1, F（000） = 1608, the final R = 0.0231 and wR = 0.0629 for 2239 observed reflections with I 〉 2a（/）. Complex 1 is a 3D pillared bilayer （4,5,7）-connected net with the Schlfli symbol of （4^14·6^7） （4^2·6^5·8^3） （4^4·6^2） topology. The photoluminescent property of 1 is also investigated.

Pd/C催化剂选择加氢合成4,4’-二氨基二苯乙烯-2,2’-二磺酸

在水介质中,采用Pd/C-OVN复合催化剂,研究了4,4’-二硝基二苯乙烯-2,2’-二磺酸(DNS)选择加氢合成4,4’-二氨基二苯乙烯-2,2’-二磺酸。用正交设计法对工艺条件进行优化,得出最佳反应条件为:原料DNS质量浓度200 g/L,Pd/C催化剂用量2.0％,助催化剂OVN用量0.8％,反应温度65℃。在此条件下考察了催化剂的稳定性,产物结构经红外光谱确证。