微波促进下3-(2-苯并呋喃基)-4-氨基-5-巯基-1,2,4-三唑及其衍生物的合成

微波辐射条件下,首先由2-苯并呋喃甲酰肼依次与二硫化碳和水合肼反应合成3-(2-苯并呋喃基)-4-氨基-5-巯基-1,2,4-三唑,进一步在微波辐射条件下由4-氨基-5-巯基-1,2,4-三唑分别与芳甲酸/芳氧基乙酸、α-溴代苯乙酮及芳醛反应以较高产率制得了相应的1,2,4-三唑并[3,4-b]-1,3,4-噻二唑、1,2,4-三唑并[3,4-b]-1,3,4-噻二嗪及4-芳亚甲基亚胺基-5-巯基-1,2,4-三唑.产物结构经IR,1HNMR,MS及元素分析进行了表征.

Thermodynamic Study and Spectroscopic Analysis of a Charge-Transfer Complex between 3,5-Diamino-1,2,4-Triazole and 6-Methyl-1,3,5-Triazine-2,4-Diamine with Chloranilic Acid

Studying of charge-transfer (CT) and proton transfer interactions is essential due to their important role in many biological field and industrial applications. The current work will add more information’s about the nature of interaction between 3,5-diamino-1,2,4-triazole (DAT) and 6-methyl-1,3,5-triazine-2,4-diamine (MTDA) with 3,6-dichloro-2,5-dihydroxy-p-benzoquinone (chloranilic acid CLA) which was studied spectrophotometrically in Ethanol (EtOH) and Methanol (MeOH) solvents at different temperatures. The molecular composition of the formed complexes was studied by applying continuous variation and spectrophotometric titration methods and found to be 1:1 charge transfer complex for both Complex (DAT:CLA) and (MTDA:CLA) which are produced. Minimum-Maximum absorbance’s method has been applied to calculate the formation constant KCT and molecular extinction coefficient (ε);they recorded high values confirming high stability of the produced complexes. Oscillator strength (f), transition dipole moment (μ), ionization potential (IP) and dissociation energy (W) of the formed CT-complexes were also determined and evaluated;they showed solvent dependency. It is concluded that the formation constant (KCT) of the complexes is found to depend on the nature of both electron acceptor and donors and on the polarity of solvents.

1-烷氧基-3-芳氧基-2-丙醇和1,3-二芳氧基-2-丙醇的合成

以 3 芳氧基 1,2 环氧丙烷与伯醇、仲醇及酚为原料 ,通过碱催化开环反应 ,区域选择性地合成 1 烷氧基 3 芳氧基 2 丙醇以及 1,3 二芳氧基 2 丙醇化合物 ,收率为 790 %～ 98% .

Synthesis, Crystal Structure, Fluorescent Property and DFT Calculations of a New Zn(Ⅱ) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole

A new coordination compound Zn（2,4＇-bpt）2（H2O）（1） based on the versatile ligand 2,4＇-Hbpt（2,4？-Hbpt = 3-（2-pyridyl）-5-（4-pyridyl）-1H-1,2,4-triazole） was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877（3）, b = 0.7483（9）, c = 1.2492（2） A, b = 92.681（2）°, V = 2230.6（4） A^3, Z = 4, Dc = 1.572 g/cm^3, m = 1.143 mm^-1, Mr = 527.85 and F（000） = 1080. The final R = 0.0581 and wR = 0.0898 with I 〉 2s（I）. 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory（DFT） were employed in order to explicate the stability and chemical reactivity of 2,4＇-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.

2-取代-1,3-二硫杂环戊烷香料的合成和香气评价

以醛／酮与1，2-乙二硫醇或1，2-丙二硫醇在对甲苯磺酸催化下反应，合成了10种2-取代-1，3-二硫杂环戊烷，产率62．8％～87．8％；其中，2-正丙基-1，3-二硫杂环戊烷产率达87．8％，纯度99．5％。经元素分析、FTIR、GC-MS和’HNMR确定了10种产物的结构。香气评价结果表明：合成的2-正丙基-1，3-二硫杂环戊烷具有花香、肉汤香气，可用于食品香精和调味料中；其余9种2-取代-1，3-二硫杂环戊烷具有肉香、葱蒜香和萝卜香。

Al_(2)O_(3)色谱柱对微量丙二烯和1,2-丁二烯测定的影响

为了解决抽余碳四组分中微量丙二烯和1,2-丁二烯的重复性较差的问题,在保证同等分离效果的前提下,对比分析Al_(2)O_(3)/S毛细管色谱柱和Al_(2)O_(3)/KCl毛细管色谱柱的出峰情况,得出结论:Al_(2)O_(3)/S毛细管色谱柱对微量丙二烯和1,2-丁二烯有较为明显的吸附现象,而Al_(2)O_(3)/KCl毛细管色谱柱对微量丙二烯和1,2-丁二烯没有明显的吸附现象,更适用于含微量丙二烯和1,2丁二烯的碳四组分的检测。

Theoretical Study on the Mechanism of a New Synthesis Reaction of 1,3,5-Substituted-1,2,4-triazoles by Carboxylic Acids,Amidines,and Hydrazines

The synthesis of 1,3,5-substituted-1,2,4-triazoles from α-imino-3-pyridine formic acid,acetamidine and anisole hydrazine as a model reaction in this paper and the synthesis mechanism of 1,3,5-substituted-1,2,4-triazole compounds from carboxylic acids,amidines and hydrazines have been first investigated with the B3 LYP/6-311＋＋G＊＊ method.According to the potential energy profile,it can be predicted that the course of the reaction consists of five reactions containing six elementary reactions.The α-imino-3-pyridine formic acid and acetamidine form first an intermediate product through a dehydration reaction; the intermediate product further combines with hydrogen ion to form a positive ion; the positive ion reacts with anisole hydrazine by a dehydration reaction to form another positive ion; then,followed by two isomerization reactions,the final reaction with the acetate ion（Ac-） produces the final product.The research results reveal the laws of synthesis reaction of 1,3,5-substituted-1,2,4-triazoles by the carboxylic acids,amidines,hydrazines and their derivatives on theoretical level.It provides the systemic theoretical basis for the synthesis,development and application of 1,3,5-substituted-1,2,4-triazole compounds.

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = trimesic acid）,has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 508.31,F（000） = 518,the final R = 0.0523 and wR = 0.0935 with I 〉 2σ（I）. In the title complex,Co（Ⅱ） ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3？-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate（AP） with complex 1 was explored by differential scanning calorimetry（DSC）. AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g^（-1）,significantly higher than that of pure AP. By Kissinger＇s method,the ratio of Ea/ln（A） is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.

Synthesis, Crystal Structure and Biological Evaluation of Acridine-1,2,3-triazole Derivatives

A series of acridine-1,2,3-triazole derivatives were designed, synthesized and characterized by NMR. 1-（2-methylacridinyl）-4-（4-methyl phenyl）-1,2,3-triazole（4f）, C_（23）H_（18）N_4, was structurally determined by single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 9.585（4）, b = 9.684（4）, c = 11.339（5） A, β = 88.250（7）o, V = 925.3（6）, Z = 2, D_c = 1.258 g/cm^3, F（000） = 368, μ = 0.077 mm^（-1）, the final R = 0.0808 and wR = 0.2218 for 3386 observed reflections（I 〉 2σ（I））. X-ray analysis indicates that the acridine ring is almost vertical to triazole ring with the dihedral angle nearly to be 75°. The crystal packing of the compound is stabilized mainly by π-π interaction. The preliminary biological tests display that some of the title compounds possess a good anti-tumour activity against MGC-803 and T24.

Synthesis and Crystal Structure of Picrates of 3,5-Diamino-1,2,4-triazole

The title compound C2N5H6＋C6N3O7H2-was synthesized by the reaction of 3,5-diamino-1,2,4-triazole and picric acid in the mixture of ethanol and water solution.Single crystals suitable for X-ray measurement were obtained at room temperature.The structure was characterized by elemental analysis and IR and determined by X-ray diffraction analysis.Crystallographic data：C8N8H8O7,Mr = 328.22,monoclinic,space group C2/c with a = 22.815（2）,b = 4.8086（5）,c = 22.564（2）,β = 93.976（2）°,V = 2469.6（4）3,Dc = 1.766 g/cm3,Z = 8,μ = 0.156 mm-1,F（000） = 1344,the final R= 0.0309,wR= 0.0864.

H_3PW_(12)O_(40)/ZrO_2-WO_3催化合成环己酮1,2-丙二醇缩酮

采用浸渍法制备了H3PW12O40/ZrO2-WO3催化剂,并通过FT-IR,XRD对其进行了表征.以H3PW12O40/ZrO2-WO3为催化剂催化合成环己酮1,2-丙二醇缩酮,研究了各种因素对收率的影响.结果表明:固定环己酮用量为0.20mol,在n(环己酮)∶n(1,2-丙二醇)=1∶1.4,反应时间30min,带水剂环己烷的用量为10mL,催化剂的用量占反应物总质量的0.8%的优化条件下,环己酮1,2-丙二醇缩酮的收率可达88.9%.

One Novel 2D Co(Ⅱ) Polymer with 1,2,3-Triazole Derivative: Crystal Structure, Fluorescence and Hirshfeld Surface Analysis

One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.

1,2-丙二醇氧化酯化制备高附加值C3化学品

以拟薄水铝石为原料,通过高温焙烧制备γ-Al_(2)O_(3),并以γ-Al_(2)O_(3)为载体,通过吸附还原法制备了3Au/γ-Al_(2)O_(3)催化剂[其中3为m(Au)∶m(催化剂)=3%]。通过TEM、XRD、ICP-OES和BET对催化剂的形貌和结构进行了表征,考察了3Au/γ-Al_(2)O_(3)催化剂在1,2-丙二醇氧化酯化制备高附加值C3化学品的催化性能。结果表明,Au颗粒的高效分散有助于提高催化剂的性能;在优选条件下,以甲醇为溶剂,无碱助剂的体系中1,2-丙二醇的转化率为63.0%,C3化学品总选择性为63.6%;并且发现增加催化剂中Au负载量,可能会影响反应的发生,从而降低主产物的选择性。

Synthesis and Crystal Structure of Ag_2(admtrz)_2(CF_3CO_2)_2(admtrz=4-amino-3,5-dimethyl-1,2,4-triazole)

The title compound (Ag2F6O4N8C12H16, Mr = 666.07) was synthesized and its crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in orthorhombic, space group Fddd with cell parameters: a = 12.2718(1), b = 23.3229(1), c = 29.1918(1) ? V = 8355.10(8) 3, Z = 16, Dc = 2.118 g/cm3, F(000) = 5184 and m = 1.966 mm-1. The structure was solved by direct methods and refined by full-matrix least-squares methods. The final R = 0.0624 and Rw = 0.1699 for 1584 observed reflections with I ≥ 2.0s(I). The molecular structure consists of two trigonal silver atoms bridged by double triazole ligands. The distance between the two silver atoms Ag(1)…Ag(1A) is 3.475(2) ?

Synthesis and Biological Activity Study of New Schiff and Mannich Base Ligands Derived from Isatin and 3-Amino-1,2,4-triazole and Their Metal Complexes

Two new Mannich and Schiff base ligands namely： （1-（3＇-amino-methyl-1＇（H）-1＇,2＇,4＇-triazole）-3-（1＇（H）-l＇,2＇,4＇- triazole-3＇-yl） iminoisatin （Lt） and l-morpholinomethyl-3-（1＇（H）-1＇,2＇,4＇-triazolyl）iminoisatin （LII） were prepared from condensation reaction of the new Schiff base 3-（l＇（H）-l＇,2＇,4＇-triazole-3＇-yl）iminoisatin （SBH） （0.01 mol） with formaldehyde and 3-amino-l,2,4-triazole （3-At） or with formaldehyde and morpholine （0.01 mole each） respectively. Structures were characterized by tH NMR, CHN analyses, mass spectra and IR spectra. Metal complexes were synthesized by heating each ligand （0.02 mo with metal salts （0.01 moo in ethanol or ethanol： acetone mixture respectively. The formula of metal complexes were suggested depending on CHN and thermal analyses, metal and chloride contents, IR and UV-visible spectra, magnetic moments （laefr） and conductivity measurements. All complexes were of octahedral geometry except palladium （II） complexes which were square planar. The two ligands and some selected metal complexes showed various antibacterial and cytotoxic effects.

Aromatic Multicarboxylate Ligands Tuned One-and Three-dimensional Zn(Ⅱ) Coordination Polymers Based on 3-(1H-pyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole

Two aromatic multicarboxylate ligands tuned Zn(Ⅱ) coordination polymers, namely, {[Zn0.5(H2L)(tp)0.5(H2O)]H2O}n(1) and {[Zn2(HL)(btc)(H2O)]H2O}n(2)(H2L = 3-(1 Hpyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole, H2tp = terephthalic acid;H3 btc = 1,3,5-benzenetricarboxylic) have been synthesized. Their structures were characterized by single-crystal X-ray diffraction analysis, elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional chain structure and is finally extended into a three-dimensional supramolecular architecture though hydrogen bonding interactions. Compound 2 shows a three-dimensional framework. Meanwhile, compounds 1 and 2 exhibit luminescent emission in the solid, and can be investigated as potential luminescent materials.

2-(1,2-亚乙/1,3-亚丙二硫)亚甲基-3-羰基丁酰氯的制备及其与芳烃的酰化反应

制备了较稳定的 2 -( 1 ,2 -亚乙 /1 ,3 -亚丙二硫 )亚甲基 -3 -羰基丁酰氯 ,并实现了其与芳烃的酰化反应 ,为 1 -芳基 -2 -( 1 ,2 -亚乙 /1 ,3 -亚丙二硫 )亚甲基 -1 ,3 -丁二酮的合成提供了一条新途径 .

固体碱催化合成3-甲胺基-1,2-丙二醇

以3-氯-1,2-丙二醇和一甲胺为原料,选用载有三乙胺的固体碱作催化剂合成3-甲胺基-1,2-丙二醇。采用正交实验和单因素分析探讨了反应的影响因素,得到最佳工艺条件为:3-氯-1,2-丙二醇与一甲胺(折算成100%)物质的量之比为1∶8,反应温度60℃,反应压力0.20 MPa,反应时间3.5 h,在该条件下3-甲胺基-1,2-丙二醇合成收率可达91.9%。通过元素分析、气相色谱、红外光谱对产物进行表征,结果证实得到了目标产物,且纯度可达99.5%以上。

3-氨基-1,2-丙二醇的合成与表征

以3-氯-1,2-丙二醇和氨水为原料合成了3-氨基-1,2-丙二醇,并引入活性炭脱色和氨回收工艺,及分子蒸馏技术。考察了原料摩尔比、反应温度和反应时间等因素对产物收率的影响,当n(氨):n(3-氯-1,2-丙二醇)=15:1,反应温度为50℃,反应时间为4 h,采用分子蒸馏分离产物时,3-氨基-1,2-丙二醇的收率为90%,产物纯度为99.6%。采用元素分析、IR、~1H NMR和^(13)C NMR对产物进行了表征。

Cr_2O_3气相催化1,1,2-三氯乙烷脱HCl性能

采用沉淀法制备了不同焙烧温度的Cr_2O_3催化剂,用于1,1,2-三氯乙烷(TCE)气相脱氯化氢制备二氯乙烯的反应。采用X射线衍射(XRD)、氢气程序升温还原(H2-TPR)、氨气程序升温脱附(NH3-TPD)、X射线光电子能谱(XPS)表征手段,研究了Cr_2O_3催化剂气相催化裂解TCE脱氯化氢反应及其反应机理。结果表明,Cr_2O_3催化剂上TCE气相脱氯化氢反应的转化率随着催化剂焙烧温度的升高逐渐降低,然而顺-1,2-二氯乙烯(cis-DCE)的选择性先增大后减小。400℃焙烧的Cr_2O_3催化剂催化性能最好,TCE转化率为70. 8%,顺-1,2-二氯乙烯的选择性为90. 0%。然而,催化剂的单位面积反应速率随着焙烧温度升高先提高后下降,400℃焙烧催化剂的单位面积反应速率为0. 801×10-2μmol/(s·m2)。催化剂的单位面积反应速率和顺-1,2-二氯乙烯(cis-DCE)的选择性与催化剂表面Cr_2O_3物种具有很好的对应关系,表明催化剂表面Cr_2O_3物种有利于脱氯化氢反应。以酸中心为活性中心计算得到的转换频率(TOF)变化趋势与单位面积反应速率相一致,400℃焙烧的催化剂的TOF为2. 82×10-5s-1,表明Cr_2O_3催化剂Cr物种合适的平均价态(～3. 20)有利于脱氯化氢反应。