5-取代-4-氨基-3-巯基-1,2,4-三唑衍生物的应用进展

5-取代-4-氨基-3-巯基-1,2,4-三唑是一类重要的五元杂环化合物,由于分子中含有巯基和伯胺基两个活性基团,既可以单个基团参与反应生成N-或S-取代产物,又可以同时发生反应生成稠杂环化合物。由其衍生而来的化合物具有广泛的生物活性,在抗菌、抗肿瘤、抗结核、抗炎镇痛、酶抑制剂、荧光探针等方面都表现出优异的性能。综述了近年来5-取代-4-氨基-3-巯基-1,2,4-三唑衍生物在医学、农业及材料领域的应用,为今后进一步研究、开发此类化合物提供参考。

脱卤杆菌介导的厌氧微生物富集菌群对1,2,4-三氯苯的降解特性

1,2,4-三氯苯是我国工业污染场地土壤和地下水中典型的有机污染物,具有持久性、生物蓄积性和高毒性特点,对生态环境和人体健康危害巨大。1,2,4-三氯苯密度比水大,容易迁移至深部厌氧区域,因此,开展1,2,4-三氯苯厌氧微生物降解与修复研究具有重要实际应用价值。本文通过长期富集培养,获得一份可以稳定地将1,2,4-三氯苯还原脱氯至1,4-二氯苯,再进一步还原脱氯至氯苯的厌氧菌液。通过16S rRNA基因扩增子测序及引物特异性的定量PCR实验,证明厚壁菌门的脱卤杆菌属细菌(Dehalobacter species)是1,2,4-三氯苯和1,4-二氯苯厌氧还原脱卤的功能菌株,其生长率为(1.68±0.8)×10^(6)copies·μmol^(-1)(释放的氯离子)。通过PCR扩增,获得Dehalobacter菌株的16S rRNA基因序列,构建了系统发育树。本研究可为1,2,4-三氯苯污染场地开展原位厌氧微生物修复提供菌株资源和理论指导。

某染料厂地块1,2,4-三氯苯污染分布特征及迁移规律

以北京某染料厂污染地块为例,对5种氯苯类(氯苯、1,2-二氯苯、1,4-二氯苯、1,2,3-三氯苯、1,2,4-三氯苯)挥发性有机污染物在土壤及地下水中的浓度数据进行统计分析。选取土壤及地下水样品中检出浓度、超标倍数较高的1,2,4-三氯苯,分析其在土壤中垂向分布特征及地下水中水平分布特征,利用GMS软件中MT3D模拟1,2,4-三氯苯在地下水中溶质迁移规律。结果表明:土壤样品中5种氯苯类有机污染物最大检出浓度均超过相应筛选值;地下水样品中氯苯、1,2-二氯苯最大检出浓度均未超过相应筛选值,1,4-二氯苯、1,2,3-三氯苯、1,2,4-三氯苯最大检出浓度均超过相应筛选值。土壤中高浓度1,2,4-三氯苯污染物主要集中在0~10 m深度范围内,地下水中1,2,4-三氯苯污染物浓度西北部明显高于东南部。地块内北侧地下水位线有轻微北移现象,各监测井地下水位处于缓慢下降趋势。地块内1,2,4-三氯苯在540 d时运移到地块南侧边界,运移距离为96.2 m。

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.

Synthesis and Crystal Structure of 2-p-Methyloxyphenyl- 3a-(2-phenyl-1,2,3-triazole-4-yl)-3,4-dihydro-1,2,4- oxa-diazolo[4,5-d][1,5] Benzothiazepine

The title compound2-p-methyloxyphenyl-3a-（2-phenyl-1,2,3-triazole-4-yl）-3,4- dihydro-1,2,4-oxa-diazolo[4,5-d][1,5] benzothiazepine （C31H25N5O2S, Mr = 531.63） has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1^- with a = 10.888（2）, b = 15.115（3）, c = 16.702（3）A, α = 99.90（3）, β = 95.21（3）, γ = 100.41（3）°, V = 2642.1（9） nm^3, Dc = 1.336 g/cm^3, Z = 4, F（000） = 1112, μ = 0.162 mm^-1 ,λ（MoKα） = 0.071073 nm, R = 0.0357 and wR = 0.1126 for 10620 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecular backbone consists of a tricyclic system with the central seven- membered ring in a twisted boat-like conformation.

1,2,4-三氟苯的合成研究进展

1,2,4-三氟苯是制备农药和医药的重要中间体。从6种不同原料角度对制备1,2,4-三氟苯的工艺路线进行综述,并对1,2,4-三氟苯的合成工艺和发展方向进行了展望。

Synthesis, Crystal Structure and Antitumor Activity of (E)-1-(7-Methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5- yl)-3-(2-methoxyphenyl)-2-(1H-1,2,4-triazol-1-yl)propenol

The title compound, （E）-1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）- 3-（2-methoxyphenyl）-2-（1H-1,2,4-triazol-1-yl）propenol （3a）, was synthesized by the Aldol con- densation reaction of 1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）-2-（1,2,4-triazol- 1-yl）ethanone with 2-methoxybenzaldehyde and then reduced with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction： monoclinic system, space group P21 with a = 6.2002（3）, b = 12.8452（7）, c = 13.2257（7） ？, Z = 2, V = 1031.23（9） ？3, Mr = 407.46, Dc = 1.312 Mg/m3, S = 1.054, μ = 0.091 mm-1, F（000） = 432, the final R = 0.0353 and wR = 0.0769 for 3161 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the title compound adopts an E configuration for the C（7）=C（8） double bond and S configuration for the chirality center with the specific rotation of –63.75°. Furthermore, the stability of the crystal was maintained through the intermolecular hydrogen bond O（1）–H？？？N（3）. The antitumor assay exhibits that the title compound 3a （E configuration） has a good antitumor activity against the Hela cell line with the IC50 value of 36.9 μM, which is better than that of 3b （Z configuration）.

Syntheses and Crystal Structures of 4-Amino-3-(3-hydroxypropyl)-1H-1,2,4-triazole-5(4H)-thione and 6-(4-Biphenylyl)-3-(3-hydroxypropyl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine

Starting with y-butyrolactone, 4-amino-3-（3-hydroxypropyl）-1H-1,2,4-triazole-5-（4H） thione 1 was prepared, and cyclization of it with 4-phenylbromoacetophenone gave 6-（4-biphenylyl）- 3-（3-hydroxypropyl）-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine Ⅱ. The structures of Ⅰ and Ⅱ were determined by elemental analyses, IR, ^1H NMR, ^13C NMR, and X-ray diffraction. Crystal data for 1： C5H10N4OS, Mr = 174.23, monoclinic system, space group P21/c, a =8.4568（6）, b = 22.8905（16）, c = 9.2625（6） A, β= 114.172（1）°, V= 1635.82（19） A^3, F（000） = 736, Z= 8, Dc = 1.415 g/cm^3, 2 λ=0.71073 A,μ = 0.346 mm^-1 and the final R = 0.0603 for 2870 unique reflections with 1993 observed ones （I 〉 2σ（I）. Crystal data for Ⅱ： C19H18N4OS, Mr = 350.43, monoclinic system, space group P21/c, a = 6.7481（7）, b = 8.2647（8）, c = 30.075（3） A, β= 94.445（2）°, V= 1672.3（3） A3, F（000） = 736, Z = 4, Dc = 1.392 g/cm^3, λ=0.71073 A,μ= 0.209 mm^-1 and the final R = 0.0667 for 3000 unique reflections with 2534 observed ones （I 〉 2σ（I））. In the crystal of compound Ⅱ, the five-membered triazole ring and two benzene rings are coplanar, while the six-membered thiadiazine ring is slightly distorted, with an r.m.s deviation of 0.227（1） A. Some hydrogen bonding interactions are observed and π-π stacking interactions between adjacent molecules are found in the packing diagrams of the two compounds.

新型1,2,4-三唑[3,4-b]-1,3,4-噻二嗪的合成及表征

以3-(2-苯基-1,2,3-三唑-4-基)-4-氨基-5-巯基-1,2,4-三唑(1)为原料分别与ω-溴代芳基乙酮、ω-溴代-ω-(1H-1,2,4-三唑-1-基)芳基乙酮反应,合成了一系列新的1,2,4-三唑[3,4-b]-1,3,4-噻二嗪类化合物2a～2e和3a～3e.其结构经IR,1HNMR和MS及元素分析确证.

A Zinc TTR Complex with a Novel 2-D Structure (TTR=3-Amino-1H-1,2,4-triazole)

The solvothermal reaction of 3-amino-1H-1,2,4-triazole （ttr） with Zn（ClO4）2·6H2O and NaCl in a 1：1：1 molar ratio gave a new complex [Zn（ttr）Cl]n with a 3-connected （4.82） 2-D structure. The layers stack in the -ABAB- way along the c axis with abundant hydrogen bonding interactions to form the crystal structure. The complex [Zn（ttr）Cl]n crystallizes in the orthorhombic space group Pbca with a = 9.369（1）, b = 10.049（1）, c = 11.905（1）A, V = 1120.9（3）A^3, Z = 8.00, C2N4H3ZnCl, Mr = 183.90, Dc = 2.180 g/cm^3,μ = 4.740 mm^-1, F（000） = 720, S = 1.059 and T = 293（2） K. The final R = 0.0662 and wR = 0.2457 for 956 observed reflections with Ⅰ〉 2σ（Ⅰ）, and R = 0.0689 and wR = 0.2504 for all data.

新型1,2,4-三唑并[3,4-b]-1,3,4-噻二嗪的波谱解析

合成了一系列新型1 ,2 ,4-三唑并[3 ,4-b]-1 ,3 ,4-噻二嗪类化合物(2 a～2 e,3 a～3 e) ,经IR,1 H NMR和MS及元素分析,确证结构无误.本文报道了化合物的波谱解析结果.

1,3-偶极环加成合成双-4,5-二氢-1,2,4-噁二唑啉衍生物

用2-苯基-1,2,3-三唑基-4-甲醛(1)或喹喔啉基-2-甲醛(2)与乙二胺缩合成双席夫碱3或4,然后与α-氯代肟在三乙胺条件下发生1,3-偶极环加成得到双-4,5-二氢-1,2,4-噁二唑啉衍生物6a～6f或7a～7f.目标化合物的结构经元素分析,IR,1HN MR和MS确认.

3,3′-偶氮1,2,4-三唑的合成

以高锰酸钾、3-氨基-1,2,4-三唑和盐酸为原料,经氧化、水洗以及无水乙醇重结晶合成了3,3′-偶氮1,2,4-三唑,采用红外光谱对产物结构进行了表征。探究了影响合成偶氮三唑的因素,优化了反应条件,最后确定适宜反应条件为:n(3-氨基-1,2,4-三唑)∶n(高锰酸钾)为1∶1.1,反应时间4 h,反应温度50℃。收率达到71.95%。

5,7-二甲基-N-芳基-1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺的合成

以5-氨基-3-巯基-1,2,4-三唑为原料,经氧氯化后分别与6个芳胺反应,得到5氨基-N-芳基1,2,4-三唑-3-磺酰胺,继而和乙酰丙酮于乙酸中环合,制得6个取代的1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺衍生物,同时讨论了胺解反应和环合反应的影响因素。所有目标产物的结构均经IR和1HNMR谱验证。

Synthesis,Crystal Structure and Biological Activity of a Novel Complex:Co(L)_2(CH_3OH)_2Cl_2 (L=3-(1,2,4-Triazole-yl)-6-chloro-pyridazine)

The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a = 6.018（3）, b = 9.832（5）, c = 9.921（5）A, a = 78.270（8）, β = 74.550（8）, γ = 83.807（8）°, V = 553.1（5）A^3, Z = 1, C14H16Cl4CoN10O2, Mr = 557.10, Dc = 1.673 g/cm^3, F（000） = 281,μ（MoKα） = 1.293 mm^-1, the final R = 0.0453 and wR = 0.1181 for 1539 observed reflections with I 〉 2σ（I）. The Co（II） ion is in a distorted centrosymmetric six-coordinate octahedral environment with two Ntriazole, two Omethanol and two Cl atoms. Via hydrogen bonds the configuration of 1 has been extended into 1D chains which are developed to 2D layers via π-π sticking action, and these layers are further extended into a 3D network by hydrogen bonds. The antibacterial activity of the title compound has been detected, and the results show that the ligands and cobalt（II） complex exhibit certain fungicidal activity against several bacteria. Furthermore, the spectral properties of the title compound have been also studied and discussed.

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.

Syntheses,Structures and Luminescent Properties of Cd(Ⅱ)/Zn(Ⅱ) Coordination Polymers Based on the Flexible 4-Substituted Bis(1,2,4-triazole) Ligand

Two new cadmium（II） and zinc（II） coordination polymers, {[Cd（btre）0.5- （mip）（H2O）2]·H2O}n （1） and [Zn（btre）（mip）]n （2）, were synthesized at room temperature condition and characterized by IR spectra, elemental analyses, single-crystal and powder X-ray diffractions （btre = 1,2-bis（1,2,4-triazol-4-yl）ethane, H2mip = 5-methyl-1,3-benzenedicarboxylic acid）. Complex 1 belongs to the triclinic system, P space group, with a = 8.9830（6）, b = 10.0579（6）, c = 10.2479（9） , α = 98.837（6）, β = 115.975（8）, γ = 106.370（6）°, V = 756.30（11） 3 and Z = 2; complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.0332（3）, b = 14.9947（7）, c = 15.9689（7） ？, β = 97.1170（10）°, V = 1671.12（13） ？3 and Z = 4. Compounds 1 and 2 based on the same N/O-donor ligands show different structures. The one-dimensional chains of 1 are further linked by hydrogen bonding and π-π interactions to yield a three-dimensional supramolecular structure. The two-dimensional （6,3） networks of 2 are further extended into a 3D framework via π-π interactions. Thermal stabilities and luminescence of 1 and 2 were investigated.

3-硝基-1,2,4-三唑-5-酮二甲胺盐(CH_3)_2NH_2^+C_2N_4O_3H^-的合成、晶体结构和量子化学研究

利用 3 硝基 1,2 ,4 三唑 5 酮 (NTO)的乙醇溶液与二甲胺的水溶液合成了NTO的二甲胺盐 (CH3 ) 2 NH+ 2 C2 N4O3 H-,在二甲基甲酰胺 (DMF)和甲醇的混合溶剂 (体积比为 1∶5 )中培养出单晶 .通过X射线单晶结构分析法测定分子结构和晶体结构 ,晶体属单斜晶系 ,空间群为P2 ( 1) /c ,晶胞参数为 :a =0 7116( 1)nm ,b =0 873 5 ( 2 )nm ,c =1 3 160 ( 3 )nm ,β =10 1 12( 2 )° ,V =0 80 2 6( 3 )nm3 ,Dc=1 45 0g/cm3 ,Z =4,F( 0 0 0 ) =3 68.采取HF/ 6 3 1+G(d)和MP2 / 6 3 1+G(d)以及B3LYP/6 3 1+G(d)方法对标题化合物进行了几何全优化 ,并对其成键情况。

含有1H-1,2,4-三唑咪唑[2,1-b]-1,3,4-噻二唑、S-三唑[3,4-b]-1,3,4-噻二唑衍生物的合成及生物活性

合成了 1 8个含有 1 H-1 ,2 ,4-三唑的咪唑 [2 ,1 -b]-1 ,3 ,4-噻二唑以及 S-三唑 [3 ,4-b]-1 ,3 ,4-噻二唑的稠杂环衍生物 ,经元素分析及谱学表征 ,探讨 2 ,5 ,6-三取代咪唑 [2 ,1 -b]-1 ,3 ,4-噻二唑的可能生成机制 .对大肠杆菌、绿脓杆菌、枯草杆菌等初步抑菌试验证明 。

3-硝仿基-5-甲基-1,2,4-三唑的合成及性能

以1,1′-二氨基-2,2′-二硝基乙烯(FOX-7)为原料,经肼解反应、酰化反应、硝化环化反应合成了3-硝仿基-5-甲基-1,2,4-三唑(MFT),三步反应收率依次为84%、64%、66%。培养出中间体1-氨基-1-(2-乙酰基肼基)-2,2-二硝基乙烯(AHADNE)、目标产物MFT的单晶并进行了解析,两种化合物的晶体密度分别为1.624g/cm^(3)、1.698g/cm^(3)。采用差示量热/热重(DSC/TG)方法对MFT的热稳定性进行表征,其热分解峰温178.7℃,热稳定性良好。通过量子化学方法对MFT进行几何构型优化,并计算得到其标准固相生成焓为99.4kJ/mol。以Kamlet-Jacob公式计算了MFT的爆轰性能,其爆速为8051m/s,爆压为28.28GPa。